Semiconductor device and manufacturing method thereof

ABSTRACT

A transistor with stable electrical characteristics. A semiconductor device includes a first insulator over a substrate, a second insulator over the first insulator, an oxide semiconductor in contact with at least part of a top surface of the second insulator, a third insulator in contact with at least part of a top surface of the oxide semiconductor, a first conductor and a second conductor electrically connected to the oxide semiconductor, a fourth insulator over the third insulator, a third conductor which is over the fourth insulator and at least part of which is between the first conductor and the second conductor, and a fifth insulator over the third conductor. The first insulator contains a halogen element.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/044,600, filed Jul. 25, 2018, now allowed, which is a continuation ofU.S. application Ser. No. 15/092,956, filed Apr. 7, 2016, now U.S. Pat.No. 10,056,497, which claims the benefit of foreign priorityapplications filed in Japan as Serial No. 2015-083163 on Apr. 15, 2015,and Serial No. 2015-110541 on May 29, 2015, all of which areincorporated by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to, for example, a transistor or asemiconductor device. The present invention relates to, for example, amethod for manufacturing a transistor or a semiconductor device. Thepresent invention relates to, for example, a display device, alight-emitting device, a lighting device, a power storage device, amemory device, a processor, or an electronic device. The presentinvention relates to a method for manufacturing a display device, aliquid crystal display device, a light-emitting device, a memory device,or an electronic device. The present invention relates to a method fordriving a display device, a liquid crystal display device, alight-emitting device, a memory device, or an electronic device.

Note that one embodiment of the present invention is not limited to theabove technical field. The technical field of one embodiment of theinvention disclosed in this specification and the like relates to anobject, a method, or a manufacturing method. In addition, one embodimentof the present invention relates to a process, a machine, manufacture,or a composition of matter.

In this specification and the like, a semiconductor device generallymeans a device that can function by utilizing semiconductorcharacteristics. A display device, a light-emitting device, a lightingdevice, an electro-optical device, a semiconductor circuit, and anelectronic device include a semiconductor device in some cases.

2. Description of the Related Art

A technique for forming a transistor by using a semiconductor over asubstrate having an insulating surface has attracted attention. Thetransistor is applied to a wide range of semiconductor devices such asan integrated circuit and a display device. Silicon is known as asemiconductor applicable to a transistor.

As silicon which is used as a semiconductor of a transistor, eitheramorphous silicon or polycrystalline silicon is used depending on thepurpose. For example, in the case of a transistor included in a largedisplay device, it is preferable to use amorphous silicon, which can beused to form a film on a large substrate with the established technique.On the other hand, in the case of a transistor included in ahigh-performance display device where driver circuits are formed overthe same substrate, it is preferred to use polycrystalline silicon,which can form a transistor having high field-effect mobility. As amethod for forming polycrystalline silicon, high-temperature heattreatment or laser light treatment which is performed on amorphoussilicon has been known.

In recent years, transistors including oxide semiconductors (typically,In—Ga—Zn oxide) have been actively developed. Oxide semiconductors havebeen researched since early times. In 1988, it was disclosed to use acrystal In—Ga—Zn oxide for a semiconductor element (see Patent Document1). In 1995, a transistor including an oxide semiconductor was invented,and its electrical characteristics were disclosed (see Patent Document2).

The transistor including an oxide semiconductor has different featuresfrom a transistor including amorphous silicon or polycrystallinesilicon. For example, a display device in which a transistor includingan oxide semiconductor is used is known to have low power consumption.An oxide semiconductor can be formed by a sputtering method or the like,and thus can be used in a transistor included in a large display device.A transistor including an oxide semiconductor has high field-effectmobility; therefore, a high-performance display device where drivercircuits are formed over the same substrate can be obtained. Inaddition, there is an advantage that capital investment can be reducedbecause part of production equipment for a transistor includingamorphous silicon can be retrofitted and utilized.

REFERENCE Patent Document

-   [Patent Document 1] Japanese Published Patent Application No.    S63-239117-   [Patent Document 2] Japanese translation of PCT international    application No. H11-505377

SUMMARY OF THE INVENTION

An object is to provide a transistor with stable electricalcharacteristics. Another object is to provide a transistor having a lowleakage current in an off state. Another object is to provide atransistor with high frequency characteristics. Another object is toprovide a transistor with normally-off electrical characteristics.Another object is to provide a transistor with a small subthresholdswing value. Another object is to provide a highly reliable transistor.

Another object is to provide a semiconductor device including thetransistor. Another object is to provide a module including thesemiconductor device. Another object is to provide an electronic deviceincluding the semiconductor device or the module. Another object is toprovide a novel semiconductor device. Another object is to provide anovel module. Another object is to provide a novel electronic device.

Note that the descriptions of these objects do not disturb the existenceof other objects. In one embodiment of the present invention, there isno need to achieve all the objects. Other objects will be apparent fromand can be derived from the description of the specification, thedrawings, the claims, and the like.

One embodiment of the present invention is a semiconductor deviceincluding a first insulator over a substrate, a second insulator overthe first insulator, an oxide semiconductor in contact with at leastpart of a top surface of the second insulator, a third insulator incontact with at least part of a top surface of the oxide semiconductor,a first conductor and a second conductor electrically connected to theoxide semiconductor, a fourth insulator over the third insulator, athird conductor which is over the fourth insulator and at least part ofwhich is between the first conductor and the second conductor, and afifth insulator over the third conductor. The first insulator contains ahalogen element.

Another embodiment of the present invention is a semiconductor devicewith the above structure, further including a sixth insulator under thefirst insulator. The sixth insulator is less permeable to hydrogen andwater than the first insulator.

Another embodiment of the present invention is a semiconductor devicewith the above structure, further including a fourth conductor betweenthe sixth insulator and the first insulator. At least part of the fourthconductor overlaps with the oxide semiconductor.

Another embodiment of the present invention is a semiconductor devicewith any of the above structures, in which the number of water moleculesreleased from the first insulator measured by thermal desorptionspectroscopy is greater than or equal to 1.0×10¹³ molecules/cm² and lessthan or equal to 1.4×10¹⁶ molecules/cm².

Another embodiment of the present invention is a semiconductor devicewith the above structure, further including a seventh insulator betweenthe fourth conductor and the first insulator. The seventh insulatorcontains hafnium.

Another embodiment of the present invention is a semiconductor devicewith the above structure, in which the number of water moleculesreleased from a stacked film of the first insulator and the seventhinsulator measured by thermal desorption spectroscopy is greater than orequal to 1.0×10¹³ molecules/cm² and less than or equal to 1.4×10¹⁶molecules/cm².

Another embodiment of the present invention is a semiconductor devicewith any of the above structures, in which the number of hydrogenmolecules released from the stacked film of the first insulator and theseventh insulator measured by thermal desorption spectroscopy is greaterthan or equal to 1.0×10¹³ molecules/cm² and less than or equal to1.2×10¹⁵ molecules/cm².

Another embodiment of the present invention is a semiconductor devicewith any of the above structures, in which the halogen element isfluorine, chlorine, or bromine.

A transistor with stable electrical characteristics can be provided. Atransistor having a low leakage current in an off state can be provided.A transistor with high frequency characteristics can be provided. Atransistor with normally-off electrical characteristics can be provided.A transistor with a small subthreshold swing value can be provided. Ahighly reliable transistor can be provided.

A semiconductor device including the transistor can be provided. Amodule including the semiconductor device can be provided. An electronicdevice including the semiconductor device or the module can be provided.A novel semiconductor device can be provided. A novel module can beprovided. A novel electronic device can be provided.

Note that the description of these effects does not disturb theexistence of other effects. One embodiment of the present invention doesnot necessarily achieve all the effects listed above. Other effects willbe apparent from and can be derived from the description of thespecification, the drawings, the claims, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1D are a top view and cross-sectional views illustrating atransistor of one embodiment of the present invention.

FIGS. 2A to 2E show structural analysis of a CAAC-OS and a singlecrystal oxide semiconductor by XRD and selected-area electrondiffraction patterns of a CAAC-OS.

FIGS. 3A to 3E show a cross-sectional TEM image and plan-view TEM imagesof a CAAC-OS and images obtained through analysis thereof.

FIGS. 4A to 4D show electron diffraction patterns and a cross-sectionalTEM image of an nc-OS.

FIGS. 5A and 5B show cross-sectional TEM images of an a-like OS.

FIG. 6 shows a change of crystal parts of an In—Ga—Zn oxide due toelectron irradiation.

FIGS. 7A to 7D are cross-sectional views illustrating transistors ofembodiments of the present invention.

FIGS. 8A to 8D are cross-sectional views illustrating transistors ofembodiments of the present invention.

FIGS. 9A and 9B are cross-sectional views illustrating a transistor ofone embodiment of the present invention.

FIGS. 10A to 10D are cross-sectional views illustrating transistors ofembodiments of the present invention.

FIGS. 11A and 11B are cross-sectional views illustrating a transistor ofone embodiment of the present invention.

FIGS. 12A to 12D are cross-sectional views illustrating transistors ofembodiments of the present invention.

FIGS. 13A to 13H are cross-sectional views illustrating a method forfabricating a transistor of one embodiment of the present invention.

FIGS. 14A to 14F are cross-sectional views illustrating a method forfabricating a transistor of one embodiment of the present invention.

FIGS. 15A to 15D are cross-sectional views illustrating a method forfabricating a transistor of one embodiment of the present invention.

FIGS. 16A and 16B are a schematic diagram and a cross-sectional viewillustrating a deposition apparatus.

FIGS. 17A to 17H are cross-sectional views illustrating a method forfabricating a transistor of one embodiment of the invention.

FIGS. 18A to 18F are cross-sectional views illustrating a method forfabricating a transistor of one embodiment of the present invention.

FIGS. 19A to 19F are cross-sectional views illustrating a method forfabricating a transistor of one embodiment of the present invention.

FIG. 20 is a top view illustrating a deposition apparatus of oneembodiment of the present invention.

FIG. 21 is a top view illustrating a chamber of one embodiment of thepresent invention.

FIG. 22 is a top view illustrating a chamber of one embodiment of thepresent invention.

FIGS. 23A and 23B are circuit diagrams illustrating semiconductordevices of embodiments of the present invention.

FIG. 24 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIG. 25 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIG. 26 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIGS. 27A to 27C are circuit diagrams illustrating memory devices ofembodiments of the present invention.

FIG. 28 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIG. 29 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIG. 30 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIG. 31 is a circuit diagram illustrating a semiconductor device of oneembodiment of the present invention.

FIG. 32 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIG. 33 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIG. 34 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIGS. 35A and 35B are top views each illustrating a semiconductor deviceof one embodiment of the present invention.

FIGS. 36A and 36B are block diagrams each illustrating a semiconductordevice of one embodiment of the present invention.

FIGS. 37A and 37B are cross-sectional views each illustrating asemiconductor device of one embodiment of the present invention.

FIGS. 38A and 38B are cross-sectional views each illustrating asemiconductor device of one embodiment of the present invention.

FIGS. 39A1, 39A2, 39A3, 39B1, 39B2, and 39B3 are perspective views andcross-sectional views of a semiconductor device of one embodiment of thepresent invention.

FIG. 40 is a block diagram illustrating a semiconductor device of oneembodiment of the present invention.

FIG. 41 is a circuit diagram of a semiconductor device of one embodimentof the present invention.

FIGS. 42A to 42C are a circuit diagram, a top view, and across-sectional view illustrating a semiconductor device of oneembodiment of the present invention.

FIGS. 43A and 43B are a circuit diagram and a cross-sectional viewillustrating a semiconductor device of one embodiment of the presentinvention.

FIGS. 44A to 44F are perspective views each illustrating an electronicdevice of one embodiment of the present invention.

FIGS. 45A to 45D are graphs showing results of TDS analysis in Example.

FIGS. 46A to 46D are graphs showing results of TDS analysis in Example.

FIGS. 47A to 47D are graphs showing results of TDS analysis in Example.

FIG. 48 is a graph showing results of ESR measurement in Example.

FIGS. 49A and 49B are graphs showing I_(d)-V_(g) characteristicsmeasured in Example.

FIG. 50 is a graph showing variations in Shift measured in Example.

FIGS. 51A to 51D are graphs showing results of stress tests in Example.

FIG. 52 is a graph showing results of deposition rate measured inExample.

FIGS. 53A and 53B are graphs showing the number of released hydrogenmolecules calculated from TDS analysis in Example.

FIGS. 54A and 54B are graphs showing the number of released watermolecules calculated from TDS analysis in Example.

FIGS. 55A to 55H are graphs showing results of TDS analysis in Example.

FIGS. 56A to 56H are graphs showing results of TDS analysis in Example.

FIGS. 57A to 57H are graphs showing results of TDS analysis in Example.

FIGS. 58A to 58H are graphs showing results of TDS analysis in Example.

FIGS. 59A to 59C are graphs showing results of SIMS measurement inExample.

FIGS. 60A to 60C are graphs showing results of SIMS measurement inExample.

FIGS. 61A to 61C are graphs showing results of XPS measurement inExample.

FIGS. 62A and 62B shows recipes for ALD performed in Example.

FIG. 63A is a graph showing results of TDS analysis in Example and FIG.63B is a graph showing the number of released water molecules calculatedfrom the graph.

FIGS. 64A and 64B show results of TDS analysis.

FIGS. 65A and 65B show the total number of released hydrogen moleculesand the total number of released water molecules, respectively,calculated from results of TDS analysis.

FIGS. 66A and 66B show results of TDS analysis.

FIGS. 67A and 67B show results of TDS analysis.

FIGS. 68A and 68B show results of TDS analysis.

FIGS. 69A and 69B show results of TDS analysis.

FIGS. 70A and 70B show the total number of released hydrogen moleculesand the total number of released water molecules, respectively,calculated from results of TDS analysis.

FIGS. 71A and 71B show the total number of released hydrogen moleculesand the total number of released water molecules, respectively,calculated from results of TDS analysis.

FIGS. 72A and 72B show the total number of released hydrogen moleculesand the total number of released water molecules, respectively,calculated from results of TDS analysis.

FIGS. 73A and 73B show the total number of released hydrogen moleculesand the total number of released water molecules, respectively,calculated from results of TDS analysis.

FIGS. 74A and 74B illustrate bonding states of a silicon oxide.

FIGS. 75A to 75C are graphs each explaining heat treatment.

FIG. 76 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIG. 77 is a cross-sectional view illustrating a semiconductor device ofone embodiment of the present invention.

FIGS. 78A to 78D are graphs showing results of stress tests in Example.

FIGS. 79A and 79B are graphs showing results of TDS analysis in Example.

FIGS. 80A and 80B are graphs showing results of TDS analysis in Example.

FIGS. 81A and 81B are graphs showing results of SIMS analysis inExample.

FIG. 82 is a graph showing results of HX-PES analysis in Example.

FIGS. 83A and 83C are graphs showing I_(d)-V_(g) characteristics, FIGS.83B and 83D are graphs showing threshold voltage and Shift, and FIG. 83Eillustrates a model of a transistor used in Example.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, embodiments and examples of the present invention will bedescribed in detail with the reference to the drawings. However, thepresent invention is not limited to the description below, and it iseasily understood by those skilled in the art that modes and detailsdisclosed herein can be modified in various ways. Furthermore, thepresent invention is not construed as being limited to description ofthe embodiments. In describing structures of the present invention withreference to the drawings, common reference numerals are used for thesame portions in different drawings. Note that the same hatched patternis applied to similar parts, and the similar parts are not especiallydenoted by reference numerals in some cases.

A structure in one of the following embodiments can be appropriatelyapplied to, combined with, or replaced with another structure in anotherembodiment, for example, and the resulting structure is also oneembodiment of the present invention.

Note that the size, the thickness of films (layers), or regions indrawings is sometimes exaggerated for simplicity.

In this specification, the terms “film” and “layer” can be interchangedwith each other.

A voltage usually refers to a potential difference between a givenpotential and a reference potential (e.g., a source potential or aground potential (GND)). A voltage can be referred to as a potential andvice versa. Note that in general, a potential (a voltage) is relativeand is determined depending on the amount relative to a certainpotential. Therefore, a potential that is represented as a “groundpotential” or the like is not always 0 V. For example, the lowestpotential in a circuit may be represented as a “ground potential.”Alternatively, a substantially intermediate potential in a circuit maybe represented as a “ground potential.” In these cases, a positivepotential and a negative potential are set using the potential as areference.

Note that the ordinal numbers such as “first” and “second” are used forconvenience and do not denote the order of steps or the stacking orderof layers.

Therefore, for example, the term “first” can be replaced with the term“second,” “third,” or the like as appropriate. In addition, the ordinalnumbers in this specification and the like do not correspond to theordinal numbers which specify one embodiment of the present invention insome cases.

Note that a “semiconductor” has characteristics of an “insulator” insome cases when the conductivity is sufficiently low, for example.Furthermore, a “semiconductor” and an “insulator” cannot be strictlydistinguished from each other in some cases because a bordertherebetween is not clear. Accordingly, a “semiconductor” in thisspecification can be called an “insulator” in some cases. Similarly, an“insulator” in this specification can be called a “semiconductor” insome cases.

Furthermore, a “semiconductor” has characteristics of a “conductor” insome cases when the conductivity is sufficiently high, for example.Furthermore, a “semiconductor” and a “conductor” cannot be strictlydistinguished from each other in some cases because a bordertherebetween is not clear. Accordingly, a “semiconductor” in thisspecification can be called a “conductor” in some cases. Similarly, a“conductor” in this specification can be called a “semiconductor” insome cases.

Note that impurities in a semiconductor refer to, for example, elementsother than the main components of the semiconductor. For example, anelement with a concentration of lower than 0.1 atomic % is an impurity.When an impurity is contained, the density of states (DOS) may be formedin a semiconductor, the carrier mobility may be decreased, or thecrystallinity may be decreased. In the case where the semiconductor isan oxide semiconductor, examples of an impurity which changescharacteristics of the semiconductor include Group 1 elements, Group 2elements, Group 14 elements, Group 15 elements, and transition metalsother than the main components; specifically, there are hydrogen(included in water), lithium, sodium, silicon, boron, phosphorus,carbon, and nitrogen, for example. In the case of an oxidesemiconductor, oxygen vacancies may be formed by entry of impuritiessuch as hydrogen. In the case where the semiconductor is silicon,examples of an impurity which changes characteristics of thesemiconductor include oxygen, Group 1 elements except hydrogen, Group 2elements, Group 13 elements, and Group 15 elements.

Note that the channel length refers to, for example, the distancebetween a source (a source region or a source electrode) and a drain (adrain region or a drain electrode) in a region where a semiconductor (ora portion where a current flows in a semiconductor when a transistor ison) and a gate electrode overlap with each other or a region where achannel is formed in a plan view of the transistor. In one transistor,channel lengths in all regions are not necessarily the same. In otherwords, the channel length of one transistor is not limited to one valuein some cases. Therefore, in this specification, the channel length isany one of values, the maximum value, the minimum value, or the averagevalue in a region where a channel is formed.

The channel width refers to, for example, the length of a portion wherea source and a drain face each other in a region where a semiconductor(or a portion where a current flows in a semiconductor when a transistoris on) and a gate electrode overlap with each other, or a region where achannel is formed. In one transistor, channel widths in all regions arenot necessarily the same. In other words, the channel width of onetransistor is not limited to one value in some cases. Therefore, in thisspecification, the channel width is any one of values, the maximumvalue, the minimum value, or the average value in a region where achannel is formed.

Note that depending on a transistor structure, a channel width in aregion where a channel is formed actually (hereinafter referred to as aneffective channel width) is different from a channel width shown in aplan view of a transistor (hereinafter referred to as an apparentchannel width) in some cases. For example, in a transistor having athree-dimensional structure, an effective channel width is greater thanan apparent channel width shown in a plan view of the transistor, andits influence cannot be ignored in some cases. For example, in aminiaturized transistor having a three-dimensional structure, theproportion of a channel region formed in a side surface of asemiconductor is high in some cases. In that case, an effective channelwidth obtained when a channel is actually formed is greater than anapparent channel width shown in the plan view.

In a transistor having a three-dimensional structure, an effectivechannel width is difficult to measure in some cases. For example, toestimate an effective channel width from a design value, it is necessaryto assume that the shape of a semiconductor is known. Therefore, in thecase where the shape of a semiconductor is not known accurately, it isdifficult to measure an effective channel width accurately.

Therefore, in this specification, in a plan view of a transistor, anapparent channel width that is a length of a portion where a source anda drain face each other in a region where a semiconductor and a gateelectrode overlap with each other is referred to as a surrounded channelwidth (SCW) in some cases. Furthermore, in this specification, in thecase where the term “channel width” is simply used, it may denote asurrounded channel width and an apparent channel width. Alternatively,in this specification, in the case where the term “channel width” issimply used, it may denote an effective channel width in some cases.Note that the values of a channel length, a channel width, an effectivechannel width, an apparent channel width, a surrounded channel width,and the like can be determined by obtaining and analyzing across-sectional TEM image and the like.

Note that in the case where field-effect mobility, a current value perchannel width, and the like of a transistor are obtained by calculation,a surrounded channel width may be used for the calculation. In thatcase, the values might be different from those calculated by using aneffective channel width.

Note that in this specification, the description “A has a shape suchthat an end portion extends beyond an end portion of B” may indicate,for example, the case where at least one of end portions of A ispositioned on an outer side than at least one of end portions of B in atop view or a cross-sectional view. Thus, the description “A has a shapesuch that an end portion extends beyond an end portion of B” can be readas the description “one end portion of A is positioned on an outer sidethan one end portion of B in a top view,” for example.

In this specification, the term “parallel” indicates that the angleformed between two straight lines is greater than or equal to −10° andless than or equal to 10°, and accordingly also includes the case wherethe angle is greater than or equal to −5° and less than or equal to 5°.A term “substantially parallel” indicates that the angle formed betweentwo straight lines is greater than or equal to −30° and less than orequal to 30°. The term “perpendicular” indicates that the angle formedbetween two straight lines is greater than or equal to 80° and less thanor equal to 100°, and accordingly also includes the case where the angleis greater than or equal to 85° and less than or equal to 95°. A term“substantially perpendicular” indicates that the angle formed betweentwo straight lines is greater than or equal to 60° and less than orequal to 120°.

In this specification, trigonal and rhombohedral crystal systems areincluded in a hexagonal crystal system.

Embodiment 1

In this embodiment, structures of semiconductor devices of embodimentsof the present invention are described with reference to FIGS. 1A to 1Dto FIGS. 12A to 12D.

<Structure of Transistor>

The structure of a transistor is described below as an example of thesemiconductor device of one embodiment of the present invention.

The structure of a transistor 10 is described with reference to FIGS. 1Ato 1C.

FIG. 1A is a top view of the transistor 10. FIG. 1B is a cross-sectionalview taken along a dashed-dotted line A1-A2 in FIG. 1A, and FIG. 1C is across-sectional view taken along a dashed-dotted line A3-A4 in FIG. 1A.A region along dashed-dotted line A1-A2 shows a structure of thetransistor 10 in the channel length direction, and a region alongdashed-dotted line A3-A4 shows a structure of the transistor 10 in thechannel width direction.

The channel length direction of a transistor refers to a direction inwhich a carrier moves between a source (a source region or a sourceelectrode) and a drain (a drain region or a drain electrode), and thechannel width direction refers to a direction perpendicular to thechannel length direction in a plane parallel to a substrate. Aninsulator 106 a, a semiconductor 106 b, and an insulator 106 c can beprovided to substantially overlap with conductors 108 a and 108 b andthe like; however, for clarity of the top view, the insulator 106 a, thesemiconductor 106 b, and the insulator 106 c are denoted with a thindashed line in FIG. 1A as being misaligned.

The transistor 10 includes an insulator 104 over a substrate 100, theinsulator 106 a over the insulator 104, the semiconductor 106 b incontact with at least part of a top surface of the insulator 106 a, theinsulator 106 c in contact with at least part of a top surface of thesemiconductor 106 b, the conductor 108 a and the conductor 108 belectrically connected to the semiconductor 106 b, an insulator 112 overthe insulator 106 c, a conductor 114 which is over the insulator 112 andat least part of which is between the conductor 108 a and the conductor108 b, and an insulator 116 over the conductor 114.

For example, as illustrated in FIGS. 1A to 1C, the transistor 10includes an insulator 101, a conductor 102, an insulator 105, aninsulator 103, and an insulator 104 that are formed over a substrate100; the insulator 106 a, the semiconductor 106 b, and the insulator 106c that are formed over the insulator 104; the conductor 108 a, theconductor 108 b, a conductor 110 a, and a conductor 110 b that areformed over the semiconductor 106 b; an insulator 112 formed over theinsulator 106 c; a conductor 114 formed over the insulator 112; and aninsulator 116, an insulator 118, a conductor 120 a, and a conductor 120b that are formed over the conductor 114.

Here, the insulator 101, the insulator 103, the insulator 104, theinsulator 105, the insulator 106 a, the insulator 106 c, the insulator112, the insulator 116, and the insulator 118 can also be referred to asinsulating films or insulating layers. The conductor 102, the conductor108 a, the conductor 108 b, the conductor 110 a, the conductor 110 b,the conductor 114, the conductor 120 a, and the conductor 120 b can alsobe referred to as conductive films or conductive layers. Thesemiconductor 106 b can also be referred to as a semiconductor film or asemiconductor layer.

Note that as the details will be described later, the insulator 106 aand the insulator 106 c are sometimes formed using a substance that canfunction as a conductor, a semiconductor, or an insulator when they areused alone. However, when the transistor is formed by stacking thesemiconductor 106 b, electrons flow in the semiconductor 106 b, in thevicinity of an interface between the semiconductor 106 b and theinsulator 106 a, and in the vicinity of an interface between thesemiconductor 106 b and the insulator 106 c, and some regions of theinsulators 106 a and 106 c do not serve as a channel of the transistor.For that reason, in the present specification and the like, theinsulators 106 a and 106 c are not referred to as conductors orsemiconductors but referred to as insulators.

The conductor 102 is formed over the insulator 101 formed over thesubstrate 100. At least part of the conductor 102 overlaps with theinsulator 106 a, the semiconductor 106 b, and the insulator 106 c. Theinsulator 105 is formed over and in contact with the conductor 102 tocover the conductor 102. The insulator 103 is formed over the insulator105, and the insulator 104 is formed over the insulator 103.

The insulator 106 a is formed over the insulator 104, and thesemiconductor 106 b is formed in contact with at least part of a topsurface of the insulator 106 a. Although end portions of the insulator106 a and the semiconductor 106 b are substantially aligned in FIG. 1B,the structure of the semiconductor device described in this embodimentis not limited to this example.

The conductor 108 a and the conductor 108 b are formed in contact withat least part of a top surface of the semiconductor 106 b. The conductor108 a and the conductor 108 b are spaced and are preferably formed toface each other with the conductor 114 provided therebetween asillustrated in FIG. 1A.

The insulator 106 c is formed in contact with at least part of the topsurface of the semiconductor 106 b. The insulator 106 c is preferably incontact with the semiconductor 106 b in a region sandwiched between theconductor 108 a and the conductor 108 b. Although the insulator 106 c isformed to cover top surfaces of the conductor 108 a and the conductor108 b in FIG. 1B, the structure of the semiconductor device described inthis embodiment is not limited to this example.

The insulator 112 is formed over the insulator 106 c. The conductor 114is formed over the insulator 112 to overlap with a region between theconductor 108 a and the conductor 108 b. Although the insulator 112 andthe insulator 106 c are formed such that end portions of the insulator112 and the insulator 106 c are substantially aligned to each other inFIG. 1B, the structure of the semiconductor device described in thisembodiment is not limited to this example.

The insulator 116 is formed over the conductor 114 and the insulator112, and the insulator 118 is formed over the insulator 116. Theconductor 120 a and the conductor 120 b are formed over the insulator118. The conductor 120 a and the conductor 120 b are connected to theconductor 108 a and the conductor 108 b through openings formed in theinsulator 106 c, the insulator 112, the insulator 116, and the insulator118.

Note that the conductor 114 may be connected to the conductor 102through an opening formed in the insulator 112, the insulator 106 c, theinsulator 104, the insulator 103, the insulator 105, and the like.

<Semiconductor>

The structure of the semiconductor 106 b is described in detail below.

In this section, the structures of the insulator 106 a and the insulator106 c are described in addition to the structure of the semiconductor106 b.

The semiconductor 106 b is an oxide semiconductor containing indium, forexample. The semiconductor 106 b can have high carrier mobility(electron mobility) by containing indium, for example. The semiconductor106 b preferably contains an element M. The element M is preferably Ti,Ga, Y, Zr, La, Ce, Nd, Sn, or Hf. Note that two or more of the aboveelements may be used in combination as the element M in some cases.

The element M is an element having high binding energy with oxygen, forexample. The element M is an element whose binding energy with oxygen ishigher than that of indium, for example. The element M is an elementthat can increase the energy gap of the oxide semiconductor, forexample. Furthermore, the semiconductor 106 b preferably contains zinc.When the oxide semiconductor contains zinc, the oxide semiconductor iseasily crystallized, in some cases.

Note that the semiconductor 106 b is not limited to the oxidesemiconductor containing indium. The semiconductor 106 b may be, forexample, an oxide semiconductor which does not contain indium andcontains zinc, an oxide semiconductor which does not contain indium andcontains gallium, or an oxide semiconductor which does not containindium and contains tin, e.g., a zinc tin oxide or a gallium tin oxide.

For example, the insulator 106 a and the insulator 106 c are oxidesemiconductors including one or more elements, or two or more elementsother than oxygen included in the semiconductor 106 b. Since theinsulator 106 a and the insulator 106 c each include one or moreelements, or two or more elements other than oxygen included in thesemiconductor 106 b, a defect state is less likely to be formed at theinterface between the insulator 106 a and the semiconductor 106 b andthe interface between the semiconductor 106 b and the insulator 106 c.

The insulator 106 a, the semiconductor 106 b, and the insulator 106 cpreferably include at least indium. In the case of using an In-M-Znoxide as the insulator 106 a, when the summation of In and M is assumedto be 100 atomic %, the proportions of In and M are preferably set to beless than 50 atomic % and greater than 50 atomic %, respectively,further preferably less than 25 atomic % and greater than 75 atomic %,respectively. In the case of using an In-M-Zn oxide as the semiconductor106 b, when the summation of In and M is assumed to be 100 atomic %, theproportions of In and M are preferably set to be greater than 25 atomic% and less than 75 atomic %, respectively, further preferably greaterthan 34 atomic % and less than 66 atomic %, respectively. In the case ofusing an In-M-Zn oxide as the insulator 106 c, when the summation of Inand M is assumed to be 100 atomic %, the proportions of In and M arepreferably set to be less than 50 atomic % and greater than 50 atomic %,respectively, further preferably less than 25 atomic % and greater than75 atomic %, respectively. Note that the insulator 106 c may be an oxidethat is of the same type as the oxide of the insulator 106 a. Note thatthe insulator 106 a and/or the insulator 106 c do/does not necessarilycontain indium in some cases. For example, the insulator 106 a and/orthe insulator 106 c may be gallium oxide or a Ga—Zn oxide. Note that theatomic ratio between the elements included in the insulator 106 a, thesemiconductor 106 b, and the insulator 106 c is not necessarily a simpleinteger ratio.

In the case of deposition using a sputtering method, typical examples ofthe atomic ratio between the metal elements of a target that is used forthe insulator 106 a or the insulator 106 c include In:M:Zn=1:2:4,In:M:Zn=1:3:2, In:M:Zn=1:3:4, In:M:Zn=1:3:6, In:M:Zn=1:3:8,In:M:Zn=1:4:3, In:M:Zn=1:4:4, In:M:Zn=1:4:5, In:M:Zn=1:4:6,In:M:Zn=1:6:3, In:M:Zn=1:6:4, In:M:Zn=1:6:5, In:M:Zn=1:6:6,In:M:Zn=1:6:7, In:M:Zn=1:6:8, In:M:Zn=1:6:9, and In:M:Zn=1:10:1. Theatomic ratio between the metal elements of the target that is used forthe insulator 106 a or the insulator 106 c may be M:Zn=10:1.

In the case of deposition using a sputtering method, typical examples ofthe atomic ratio between the metal elements of a target that is used forthe semiconductor 106 b include In:M:Zn=1:1:1, In:M:Zn=1:1:1.2,In:M:Zn=2:1:1.5, In:M:Zn=2:1:2.3, In:M:Zn=2:1:3, In:M:Zn=3:1:2,In:M:Zn=4:2:4.1, and In:M:Zn=5:1:7. In particular, when a sputteringtarget containing In, Ga, and Zn at an atomic ratio of 4:2:4.1 is used,the deposited semiconductor 106 b may contain In, Ga, and Zn at anatomic ratio of around 4:2:3.

An indium gallium oxide has small electron affinity and a highoxygen-blocking property. Therefore, the insulator 106 c preferablyincludes an indium gallium oxide. The gallium atomic ratio [Ga/(In+Ga)]is, for example, higher than or equal to 70%, preferably higher than orequal to 80%, further preferably higher than or equal to 90%.

For the semiconductor 106 b, an oxide with a wide energy gap may beused, for example. For example, the energy gap of the semiconductor 106b is greater than or equal to 2.5 eV and less than or equal to 4.2 eV,preferably greater than or equal to 2.8 eV and less than or equal to 3.8eV, further preferably greater than or equal to 3 eV and less than orequal to 3.5 eV. Here, the energy gap of the insulator 106 a is largerthan that of the semiconductor 106 b. The energy gap of the insulator106 c is larger than that of the semiconductor 106 b.

As the semiconductor 106 b, an oxide having an electron affinity largerthan those of the insulators 106 a and 106 c is used. For example, asthe semiconductor 106 b, an oxide having an electron affinity largerthan those of the insulators 106 a and 106 c by 0.07 eV or higher and1.3 eV or lower, preferably 0.1 eV or higher and 0.7 eV or lower,further preferably 0.15 eV or higher and 0.4 eV or lower is used. Notethat the electron affinity refers to an energy difference between thevacuum level and the conduction band minimum. In other words, the energylevel of the conduction band minimum of the insulator 106 a or theinsulator 106 c is closer to the vacuum level than the energy level ofthe conduction band minimum of the semiconductor 106 b is.

By applying gate voltage at this time, a channel is formed in thesemiconductor 106 b having the largest electron affinity among theinsulator 106 a, the semiconductor 106 b, and the insulator 106 c. Notethat when a high gate voltage is applied, current also flows in theinsulator 106 a near the interface with the semiconductor 106 b and inthe insulator 106 c near the interface with the semiconductor 106 b insome cases.

The insulator 106 a and the insulator 106 c are formed using a substancethat can function as a conductor, a semiconductor, or an insulator whenthey are used alone. However, when the transistor is formed using astack including the insulator 106 a, the semiconductor 106 b, and theinsulator 106 c, electrons flow in the semiconductor 106 b, at and inthe vicinity of the interface between the semiconductor 106 b and theinsulator 106 a, and at and in the vicinity of the interface between thesemiconductor 106 b and the insulator 106 c; thus, the insulator 106 aand the insulator 106 c have a region not functioning as a channel ofthe transistor. For that reason, in this specification and the like, theinsulator 106 a and the insulator 106 c are not referred to as asemiconductor but an insulator. Note that the reason why the insulator106 a and the insulator 106 c are referred to as an insulator is becausethey are closer to an insulator than the semiconductor 106 b is in termsof their functions in the transistor; thus, a substance that can be usedfor the semiconductor 106 b is used for the insulator 106 a and theinsulator 106 c in some cases.

Here, in some cases, there is a mixed region of the insulator 106 a andthe semiconductor 106 b between the insulator 106 a and thesemiconductor 106 b. Furthermore, in some cases, there is a mixed regionof the semiconductor 106 b and the insulator 106 c between thesemiconductor 106 b and the insulator 106 c. The mixed region has a lowdensity of defect states. For that reason, the stacked film of theinsulator 106 a, the semiconductor 106 b, and the insulator 106 c has aband structure where energy is changed continuously at each interfaceand in the vicinity of the interface (continuous junction). Note thatthe boundary between the insulator 106 a and the semiconductor 106 b andthe boundary between the insulator 106 c and the semiconductor 106 b arenot clear in some cases.

At this time, electrons move mainly in the semiconductor 106 b, not inthe insulator 106 a and the insulator 106 c. As described above, whenthe density of defect states at the interface between the insulator 106a and the semiconductor 106 b and the density of defect states at theinterface between the semiconductor 106 b and the insulator 106 c aredecreased, electron movement in the semiconductor 106 b is less likelyto be inhibited and the on-state current of the transistor can beincreased.

As factors in inhibiting electron movement are decreased, the on-statecurrent of the transistor can be increased. For example, in the casewhere there is no factor in inhibiting electron movement, electrons areassumed to be efficiently moved. Electron movement is inhibited, forexample, in the case where physical unevenness of the channel formationregion is large.

To increase the on-state current of the transistor, for example, rootmean square (RMS) roughness with a measurement area of 1 μm×1 μm of thetop or bottom surface of the semiconductor 106 b (a formation surface;here, the top surface of the insulator 106 a) is less than 1 nm,preferably less than 0.6 nm, further preferably less than 0.5 nm, stillfurther preferably less than 0.4 nm. The average surface roughness (alsoreferred to as Ra) with the measurement area of 1 μm×1 μm is less than 1nm, preferably less than 0.6 nm, further preferably less than 0.5 nm,still further preferably less than 0.4 nm. The maximum difference (P−V)with the measurement area of 1 μm×1 μm is less than 10 nm, preferablyless than 9 nm, further preferably less than 8 nm, still furtherpreferably less than 7 nm. RMS roughness, Ra, and P−V can be measuredusing a scanning probe microscope SPA-500 manufactured by SII NanoTechnology Inc.

Moreover, the thickness of the insulator 106 c is preferably as small aspossible to increase the on-state current of the transistor. It ispreferable that the thickness of the insulator 106 c is smaller thanthat of the insulator 106 a and smaller than that of the semiconductor106 b. For example, the insulator 106 c is formed to include a regionhaving a thickness of less than 10 nm, preferably less than or equal to5 nm, further preferably less than or equal to 3 nm. Meanwhile, theinsulator 106 c has a function of blocking entry of elements other thanoxygen (such as hydrogen and silicon) included in the adjacent insulatorinto the semiconductor 106 b where a channel is formed. For this reason,it is preferable that the insulator 106 c have a certain thickness. Forexample, the insulator 106 c is formed to include a region having athickness of greater than or equal to 0.3 nm, preferably greater than orequal to 1 nm, further preferably greater than or equal to 2 nm.

To improve reliability, the insulator 106 a is preferably thick. Forexample, the insulator 106 a includes a region with a thickness of, forexample, greater than or equal to 10 nm, preferably greater than orequal to 20 nm, further preferably greater than or equal to 40 nm, stillfurther preferably greater than or equal to 60 nm. When the thickness ofthe insulator 106 a is made large, a distance from the interface betweenthe adjacent insulator and the insulator 106 a to the semiconductor 106b in which a channel is formed can be large. Since the productivity ofthe semiconductor device might be decreased, the insulator 106 a has aregion with a thickness of, for example, less than or equal to 200 nm,preferably less than or equal to 120 nm, further preferably less than orequal to 80 nm.

Silicon in the oxide semiconductor might serve as a carrier trap or acarrier generation source, for example. Thus, the silicon concentrationin the semiconductor 106 b is preferably as low as possible. Forexample, between the semiconductor 106 b and the insulator 106 a, aregion with a silicon concentration measured by secondary ion massspectrometry (SIMS) of higher than or equal to 1×10¹⁶ atoms/cm³ andlower than or equal to 1×10¹⁹ atoms/cm³, preferably higher than or equalto 1×10¹⁶ atoms/cm³ and lower than or equal to 5×10¹⁸ atoms/cm³, andfurther preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lowerthan or equal to 2×10¹⁸ atoms/cm³ is provided. Furthermore, between thesemiconductor 106 b and the insulator 106 c, a region with a siliconconcentration measured by SIMS of higher than or equal to 1×10¹⁶atoms/cm³ and lower than or equal to 1×10¹⁹ atoms/cm³, preferably higherthan or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 5×10¹⁸atoms/cm³, further preferably higher than or equal to 1×10¹⁶ atoms/cm³and lower than or equal to 2×10¹⁸ atoms/cm³ is provided.

It is preferable to reduce the hydrogen concentration in the insulator106 a and the insulator 106 c in order to reduce the hydrogenconcentration in the semiconductor 106 b. The insulator 106 a and theinsulator 106 c each include a region with a hydrogen concentrationmeasured by SIMS of higher than or equal to 1×10¹⁶ atoms/cm³ and lowerthan or equal to 2×10²⁰ atoms/cm³, preferably higher than or equal to1×10¹⁶ atoms/cm³ and lower than or equal to 5×10¹⁹ atoms/cm³, furtherpreferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than orequal to 1×10¹⁹ atoms/cm³, or still further preferably higher than orequal to 1×10¹⁶ atoms/cm³ and lower than or equal to 5×10¹⁸ atoms/cm³.It is preferable to reduce the nitrogen concentration in the insulator106 a and the insulator 106 c in order to reduce the nitrogenconcentration in the semiconductor 106 b. The insulator 106 a and theinsulator 106 c each include a region with a nitrogen concentrationmeasured by SIMS of higher than or equal to 1×10¹⁵ atoms/cm³ and lowerthan or equal to 5×10¹⁹ atoms/cm³, preferably higher than or equal to1×10¹⁵ atoms/cm³ and lower than or equal to 5×10¹⁸ atoms/cm³, furtherpreferably higher than or equal to 1×10¹⁵ atoms/cm³ and lower than orequal to 1×10¹⁸ atoms/cm³, or still further preferably higher than orequal to 1×10¹⁵ atoms/cm³ and lower than or equal to 5×10¹⁷ atoms/cm³.

Each of the insulator 106 a, the semiconductor 106 b, and the insulator106 c described in this embodiment, especially the semiconductor 106 b,is an oxide semiconductor with a low impurity concentration and a lowdensity of defect states (a small number of oxygen vacancies) and thuscan be referred to as a highly purified intrinsic or substantiallyhighly purified intrinsic oxide semiconductor. Since a highly purifiedintrinsic or substantially highly purified intrinsic oxide semiconductorhas few carrier generation sources, the carrier density can be low.Thus, a transistor in which a channel region is formed in the oxidesemiconductor rarely has a negative threshold voltage (is rarelynormally on). A highly purified intrinsic or substantially highlypurified intrinsic oxide semiconductor has a low density of defectstates and accordingly has a low density of trap states in some cases.Furthermore, a highly purified intrinsic or substantially highlypurified intrinsic oxide semiconductor has an extremely low off-statecurrent; the off-state current can be less than or equal to themeasurement limit of a semiconductor parameter analyzer, i.e., less thanor equal to 1×10⁻¹³ A, at a voltage (drain voltage) between a sourceelectrode and a drain electrode of from 1 V to 10 V even when an elementhas a channel width (W) of 1×10⁶ μm and a channel length (L) of 10 μm.

Accordingly, the transistor in which the channel region is formed in thehighly purified intrinsic or substantially highly purified intrinsicoxide semiconductor can have a small change in electricalcharacteristics and high reliability. Charges trapped by the trap statesin the oxide semiconductor take a long time to be released and maybehave like fixed charges. Thus, the transistor whose channel region isformed in the oxide semiconductor having a high density of trap stateshas unstable electrical characteristics in some cases. Examples ofimpurities are hydrogen, nitrogen, alkali metal, and alkaline earthmetal.

Hydrogen contained in the insulator 106 a, the semiconductor 106 b, andthe insulator 106 c reacts with oxygen bonded to a metal atom to bewater, and also causes an oxygen vacancy in a lattice from which oxygenis released (or a portion from which oxygen is released). Due to entryof hydrogen into the oxygen vacancy, an electron serving as a carrier isgenerated in some cases. Furthermore, in some cases, bonding of part ofhydrogen to oxygen bonded to a metal atom causes generation of anelectron serving as a carrier. Hydrogen trapped by an oxygen vacancymight form a shallow donor level in a band structure of a semiconductor.Thus, a transistor including an oxide semiconductor that containshydrogen is likely to be normally on. For this reason, it is preferablethat hydrogen be reduced as much as possible in the insulator 106 a, thesemiconductor 106 b, and the insulator 106 c. Specifically, the hydrogenconcentration in the insulator 106 a, the semiconductor 106 b, and theinsulator 106 c, which is measured by SIMS, is lower than or equal to2×10²⁰ atoms/cm³, preferably lower than or equal to 5×10¹⁹ atoms/cm³,further preferably lower than or equal to 1×10¹⁹ atoms/cm³, stillfurther preferably lower than or equal to 5×10¹⁸ atoms/cm³, yet furtherpreferably lower than or equal to 1×10¹⁸ atoms/cm³, even furtherpreferably lower than or equal to 5×10¹⁷ atoms/cm³, and furtherpreferably lower than or equal to 1×10¹⁶ atoms/cm³.

When the insulator 106 a, the semiconductor 106 b, and the insulator 106c contain silicon or carbon, which is one of elements belonging to Group14, oxygen vacancies in the insulator 106 a, the semiconductor 106 b,and the insulator 106 c are increased, which makes the insulator 106 a,the semiconductor 106 b, and the insulator 106 c n-type. Thus, theconcentration of silicon or carbon (measured by SIMS) in the insulator106 a, the semiconductor 106 b, and the insulator 106 c or theconcentration of silicon or carbon (measured by SIMS) at and in thevicinity of the interface with the insulator 106 a, the semiconductor106 b, and the insulator 106 c is set to be lower than or equal to2×10¹⁸ atoms/cm³, preferably lower than or equal to 2×10¹⁷ atoms/cm³.

In addition, the concentration of an alkali metal or alkaline earthmetal in the insulator 106 a, the semiconductor 106 b, and the insulator106 c, which is measured by SIMS, is set to be lower than or equal to1×10¹⁸ atoms/cm³, preferably lower than or equal to 2×10¹⁶ atoms/cm³. Analkali metal and an alkaline earth metal might generate carriers whenbonded to an oxide semiconductor, in which case the off-state current ofthe transistor might be increased. Thus, it is preferable to reduce theconcentration of an alkali metal or alkaline earth metal in theinsulator 106 a, the semiconductor 106 b, and the insulator 106 c.

Furthermore, when containing nitrogen, the insulator 106 a, thesemiconductor 106 b, and the insulator 106 c easily become n-type bygeneration of electrons serving as carriers and an increase of carrierdensity. Thus, a transistor including an oxide semiconductor film whichcontains nitrogen is likely to have normally-on characteristics. Forthis reason, nitrogen in the oxide semiconductor film is preferablyreduced as much as possible; the concentration of nitrogen which ismeasured by SIMS is preferably set to be, for example, lower than orequal to 5×10¹⁸ atoms/cm³.

FIG. 1D is an enlarged cross-sectional view illustrating the middleportion of the insulator 106 a and the semiconductor 106 b and thevicinity of the middle portion. As illustrated in FIGS. 1B and 1D,regions of the semiconductor 106 b and the insulator 106 c that are incontact with the conductor 108 a and the conductor 108 b (which aredenoted with dotted lines in FIGS. 1B and 1D) include a low-resistanceregion 109 a and a low-resistance region 109 b in some cases. Thelow-resistance region 109 a and the low-resistance region 109 b aremainly formed when oxygen is extracted by the conductor 108 a and theconductor 108 b that are in contact with the semiconductor 106 b, orwhen a conductive material in the conductor 108 a or the conductor 108 bis bonded to an element in the semiconductor 106 b. The formation of thelow-resistance region 109 a and the low-resistance region 109 b leads toa reduction in contact resistance between the conductor 108 a or 108 band the semiconductor 106 b, whereby the transistor 10 can have highon-state current.

Although not illustrated, a low-resistance region is sometimes formed inregions of the insulator 106 a that are in contact with the conductor108 a or the conductor 108 b. In the following drawings, a dotted linedenotes a low-resistance region.

As illustrated in FIG. 1D, the semiconductor 106 b might have a smallerthickness in a region between the conductor 108 a and the conductor 108b than in regions overlapping with the conductor 108 a and the conductor108 b. This is because part of the top surface of the semiconductor 106b is removed at the time of formation of the conductor 108 a and theconductor 108 b. In formation of the conductor to be the conductor 108 aand the conductor 108 b, a region with low resistance like thelow-resistance regions 109 a and 109 b is formed on the top surface ofthe semiconductor 106 b in some cases. By removal of a region of the topsurface of the semiconductor 106 b that is positioned between theconductor 108 a and the conductor 108 b, the channel can be preventedfrom being formed in the low-resistance region on the top surface of thesemiconductor 106 b. In the drawings, even when a thin region is notdrawn in an enlarged view or the like, such a thin region might beformed.

Note that the above-described three-layer structure of the insulator 106a, the semiconductor 106 b, and the insulator 106 c is an example. Forexample, a two-layer structure without the insulator 106 a or theinsulator 106 c may be employed. Alternatively, a single-layer structureincluding neither the insulator 106 a nor the insulator 106 c may beemployed. Alternatively, an n-layer structure (n is an integer of 4 ormore) including one or more layers in addition to the insulator 106 a,the semiconductor 106 b, and the insulator 106 c may be employed. Theadded layer may be formed with any of materials used for the insulator106 a, the semiconductor 106 b, and the insulator 106 c.

<Structure of Oxide Semiconductor>

A structure of an oxide semiconductor is described below.

An oxide semiconductor is classified into a single crystal oxidesemiconductor and a non-single-crystal oxide semiconductor. Examples ofa non-single-crystal oxide semiconductor include a c-axis alignedcrystalline oxide semiconductor (CAAC-OS), a polycrystalline oxidesemiconductor, a nanocrystalline oxide semiconductor (nc-OS), anamorphous-like oxide semiconductor (a-like OS), and an amorphous oxidesemiconductor.

From another perspective, an oxide semiconductor is classified into anamorphous oxide semiconductor and a crystalline oxide semiconductor.Examples of a crystalline oxide semiconductor include a single crystaloxide semiconductor, a CAAC-OS, a polycrystalline oxide semiconductor,and an nc-OS.

An amorphous structure is generally thought to be isotropic and have nonon-uniform structure, to be metastable and not have fixed positions ofatoms, to have a flexible bond angle, and to have a short-range orderbut have no long-range order, for example.

In other words, a stable oxide semiconductor cannot be regarded as acompletely amorphous oxide semiconductor. Moreover, an oxidesemiconductor that is not isotropic (e.g., an oxide semiconductor thathas a periodic structure in a microscopic region) cannot be regarded asa completely amorphous oxide semiconductor. In contrast, an a-like OS,which is not isotropic, has an unstable structure that contains a void.Because of its instability, an a-like OS is close to an amorphous oxidesemiconductor in terms of physical properties.

<CAAC-OS>

First, a CAAC-OS is described.

A CAAC-OS is one of oxide semiconductors having a plurality of c-axisaligned crystal parts (also referred to as pellets).

Analysis of a CAAC-OS by X-ray diffraction (XRD) is described. Forexample, when the structure of a CAAC-OS including an InGaZnO₄ crystalthat is classified into the space group R-3m is analyzed by anout-of-plane method, a peak appears at a diffraction angle (2θ) ofaround 31° as shown in FIG. 2A. This peak is derived from the (009)plane of the InGaZnO₄ crystal, which indicates that crystals in theCAAC-OS have c-axis alignment, and that the c-axes are aligned in adirection substantially perpendicular to a surface over which a CAAC-OSfilm is formed (also referred to as a formation surface) or a topsurface of the CAAC-OS film. Note that a peak sometimes appears at a ofaround 36° in addition to the peak at a 2θ of around 31°. The peak at a2θ of around 36° is derived from a crystal structure classified into thespace group Fd-3m. Therefore, it is preferable that the CAAC-OS do notshow the peak.

On the other hand, in structural analysis of the CAAC-OS by an in-planemethod in which an X-ray is incident on the CAAC-OS in a directionparallel to the formation surface, a peak appears at a 2θ of around 56°.This peak is attributed to the (110) plane of the InGaZnO₄ crystal. Whenanalysis (ϕ scan) is performed with 2—0 fixed at around 56° and with thesample rotated using a normal vector to the sample surface as an axis (ϕaxis), as shown in FIG. 2B, a peak is not clearly observed. In contrast,in the case where single crystal InGaZnO₄ is subjected to ϕ scan with 2θfixed at around 56°, as shown in FIG. 2C, six peaks which are derivedfrom crystal planes equivalent to the (110) plane are observed.Accordingly, the structural analysis using XRD shows that the directionsof a-axes and b-axes are irregularly oriented in the CAAC-OS.

Next, a CAAC-OS analyzed by electron diffraction is described. Forexample, when an electron beam with a probe diameter of 300 nm isincident on a CAAC-OS including an InGaZnO₄ crystal in a directionparallel to the formation surface of the CAAC-OS, a diffraction pattern(also referred to as a selected-area electron diffraction pattern) shownin FIG. 2D can be obtained. In this diffraction pattern, spots derivedfrom the (009) plane of an InGaZnO₄ crystal are included. Thus, theelectron diffraction also indicates that pellets included in the CAAC-OShave c-axis alignment and that the c-axes are aligned in a directionsubstantially perpendicular to the formation surface or the top surfaceof the CAAC-OS. Meanwhile, FIG. 2E shows a diffraction pattern obtainedin such a manner that an electron beam with a probe diameter of 300 nmis incident on the same sample in a direction perpendicular to thesample surface. As shown in FIG. 2E, a ring-like diffraction pattern isobserved. Thus, the electron diffraction using an electron beam with aprobe diameter of 300 nm also indicates that the a-axes and b-axes ofthe pellets included in the CAAC-OS do not have regular orientation. Thefirst ring in FIG. 2E is considered to be derived from the (010) plane,the (100) plane, and the like of the InGaZnO₄ crystal. The second ringin FIG. 2E is considered to be derived from the (110) plane and thelike.

In a combined analysis image (also referred to as a high-resolution TEMimage) of a bright-field image and a diffraction pattern of a CAAC-OS,which is obtained using a transmission electron microscope (TEM), aplurality of pellets can be observed. However, even in thehigh-resolution TEM image, a boundary between pellets, that is, a grainboundary is not clearly observed in some cases. Thus, in the CAAC-OS, areduction in electron mobility due to the grain boundary is less likelyto occur.

FIG. 3A shows a high-resolution TEM image of a cross section of theCAAC-OS which is observed from a direction substantially parallel to thesample surface. The high-resolution TEM image is obtained with aspherical aberration corrector function. The high-resolution TEM imageobtained with a spherical aberration corrector function is particularlyreferred to as a Cs-corrected high-resolution TEM image. TheCs-corrected high-resolution TEM image can be observed with, forexample, an atomic resolution analytical electron microscope JEM-ARM200Fmanufactured by JEOL Ltd.

FIG. 3A shows pellets in which metal atoms are arranged in a layeredmanner. FIG. 3A proves that the size of a pellet is greater than orequal to 1 nm or greater than or equal to 3 nm. Therefore, the pelletcan also be referred to as a nanocrystal (nc). Furthermore, the CAAC-OScan also be referred to as an oxide semiconductor including c-axisaligned nanocrystals (CANC). A pellet reflects unevenness of a formationsurface or a top surface of the CAAC-OS, and is parallel to theformation surface or the top surface of the CAAC-OS.

FIGS. 3B and 3C show Cs-corrected high-resolution TEM images of a planeof the CAAC-OS observed from a direction substantially perpendicular tothe sample surface. FIGS. 3D and 3E are images obtained through imageprocessing of FIGS. 3B and 3C. The method of image processing is asfollows. The image in FIG. 3B is subjected to fast Fourier transform(FFT), so that an FFT image is obtained. Then, mask processing isperformed such that a range of from 2.8 nm⁻¹ to 5.0 nm⁻¹ from the originin the obtained FFT image remains. After the mask processing, the FFTimage is processed by inverse fast Fourier transform (IFFT) to obtain aprocessed image. The image obtained in this manner is called an FFTfiltering image. The FFT filtering image is a Cs-correctedhigh-resolution TEM image from which a periodic component is extracted,and shows a lattice arrangement.

In FIG. 3D, a portion where a lattice arrangement is broken is denotedwith a dashed line. A region surrounded by a dashed line is one pellet.The portion denoted with the dashed line is a junction of pellets. Thedashed line draws a hexagon, which means that the pellet has a hexagonalshape. Note that the shape of the pellet is not always a regular hexagonbut is a non-regular hexagon in many cases.

In FIG. 3E, a dotted line denotes a portion between a region where alattice arrangement is well aligned and another region where a latticearrangement is well aligned, and dashed lines denote the directions ofthe lattice arrangements. A clear crystal grain boundary cannot beobserved even in the vicinity of the dotted line. When a lattice pointin the vicinity of the dotted line is regarded as a center andsurrounding lattice points are joined, a distorted hexagon, pentagon,and/or heptagon can be formed, for example. That is, a latticearrangement is distorted so that formation of a crystal grain boundaryis inhibited. This is probably because the CAAC-OS can toleratedistortion owing to a low density of the atomic arrangement in an a-bplane direction, an interatomic bond distance changed by substitution ofa metal element, and the like.

As described above, the CAAC-OS has c-axis alignment, its pellets(nanocrystals) are connected in an a-b plane direction, and the crystalstructure has distortion. For this reason, the CAAC-OS can also bereferred to as an oxide semiconductor including a c-axis-aligneda-b-plane-anchored (CAA) crystal.

The CAAC-OS is an oxide semiconductor with high crystallinity. Entry ofimpurities, formation of defects, or the like might decrease thecrystallinity of an oxide semiconductor. This means that the CAAC-OS hassmall amounts of impurities and defects (e.g., oxygen vacancies).

Note that the impurity means an element other than the main componentsof the oxide semiconductor, such as hydrogen, carbon, silicon, or atransition metal element. For example, an element (specifically, siliconor the like) having higher strength of bonding to oxygen than a metalelement included in an oxide semiconductor extracts oxygen from theoxide semiconductor, which results in disorder of the atomic arrangementand reduced crystallinity of the oxide semiconductor. A heavy metal suchas iron or nickel, argon, carbon dioxide, or the like has a large atomicradius (or molecular radius), and thus disturbs the atomic arrangementof the oxide semiconductor and decreases crystallinity.

The characteristics of an oxide semiconductor having impurities ordefects might be changed by light, heat, or the like. Impuritiescontained in the oxide semiconductor might serve as carrier traps orcarrier generation sources, for example. Furthermore, oxygen vacanciesin the oxide semiconductor serve as carrier traps or serve as carriergeneration sources when hydrogen is captured therein.

The CAAC-OS having small amounts of impurities and oxygen vacancies isan oxide semiconductor with low carrier density (specifically, lowerthan 8×10¹¹/cm³, preferably lower than 1×10¹¹/cm³, further preferablylower than 1×10¹⁰/cm³, and is higher than or equal to 1×10⁻⁹/cm³). Suchan oxide semiconductor is referred to as a highly purified intrinsic orsubstantially highly purified intrinsic oxide semiconductor. A CAAC-OShas a low impurity concentration and a low density of defect states.Thus, the CAAC-OS can be referred to as an oxide semiconductor havingstable characteristics.

<nc-OS>

Next, an nc-OS is described.

Analysis of an nc-OS by XRD is described. When the structure of an nc-OSis analyzed by an out-of-plane method, a peak indicating orientationdoes not appear. That is, a crystal of an nc-OS does not haveorientation.

For example, when an electron beam with a probe diameter of 50 nm isincident on a 34-nm-thick region of thinned nc-OS including an InGaZnO₄crystal in a direction parallel to the formation surface, a ring-shapeddiffraction pattern (a nanobeam electron diffraction pattern) shown inFIG. 4A is observed. FIG. 4B shows a diffraction pattern obtained whenan electron beam with a probe diameter of 1 nm is incident on the samesample. As shown in FIG. 4B, a plurality of spots are observed in aring-like region. In other words, ordering in an nc-OS is not observedwith an electron beam with a probe diameter of 50 nm but is observedwith an electron beam with a probe diameter of 1 nm.

Furthermore, an electron diffraction pattern in which spots are arrangedin an approximately hexagonal shape is observed in some cases as shownin FIG. 4C when an electron beam having a probe diameter of 1 nm isincident on a region with a thickness of less than 10 nm. This meansthat an nc-OS has a well-ordered region, i.e., a crystal, in the rangeof less than 10 nm in thickness. Note that an electron diffractionpattern having regularity is not observed in some regions becausecrystals are aligned in various directions.

FIG. 4D shows a Cs-corrected high-resolution TEM image of a crosssection of an nc-OS observed from the direction substantially parallelto the formation surface. In a high-resolution TEM image, an nc-OS has aregion in which a crystal part is observed, such as the part indicatedby additional lines in FIG. 4D, and a region in which a crystal part isnot clearly observed. In most cases, the size of a crystal part includedin the nc-OS is greater than or equal to 1 nm and less than or equal to10 nm, or specifically, greater than or equal to 1 nm and less than orequal to 3 nm. Note that an oxide semiconductor including a crystal partwhose size is greater than 10 nm and less than or equal to 100 nm issometimes referred to as a microcrystalline oxide semiconductor. In ahigh-resolution TEM image of the nc-OS, for example, a grain boundary isnot clearly observed in some cases. Note that there is a possibilitythat the origin of the nanocrystal is the same as that of a pellet in aCAAC-OS. Therefore, a crystal part of the nc-OS may be referred to as apellet in the following description.

In the nc-OS, a microscopic region (for example, a region with a sizegreater than or equal to 1 nm and less than or equal to 10 nm, inparticular, a region with a size greater than or equal to 1 nm and lessthan or equal to 3 nm) has a periodic atomic arrangement. There is noregularity of crystal orientation between different pellets in thenc-OS. Thus, the orientation of the whole film is not ordered.Accordingly, the nc-OS cannot be distinguished from an a-like OS or anamorphous oxide semiconductor, depending on an analysis method.

Since there is no regularity of crystal orientation between the pellets(nanocrystals), the nc-OS can also be referred to as an oxidesemiconductor including random aligned nanocrystals (RANC) or an oxidesemiconductor including non-aligned nanocrystals (NANC).

The nc-OS is an oxide semiconductor that has high regularity as comparedwith an amorphous oxide semiconductor. Therefore, the nc-OS is likely tohave a lower density of defect states than an a-like OS and an amorphousoxide semiconductor. Note that there is no regularity of crystalorientation between different pellets in the nc-OS. Therefore, the nc-OShas a higher density of defect states than the CAAC-OS.

<A-Like OS>

An a-like OS has a structure intermediate between those of the nc-OS andthe amorphous oxide semiconductor.

FIGS. 5A and 5B are high-resolution cross-sectional TEM images of ana-like OS. FIG. 5A is the high-resolution cross-sectional TEM image ofthe a-like OS at the start of the electron irradiation. FIG. 5B is thehigh-resolution cross-sectional TEM image of a-like OS after theelectron (e⁻) irradiation at 4.3×10⁸ e⁻/nm². FIGS. 5A and 5B show thatstripe-like bright regions extending vertically are observed in thea-like OS from the start of the electron irradiation. It can be alsofound that the shape of the bright region changes after the electronirradiation. Note that the bright region is presumably a void or alow-density region.

The a-like OS has an unstable structure because it contains a void. Toverify that an a-like OS has an unstable structure as compared with aCAAC-OS and an nc-OS, a change in structure caused by electronirradiation is described below.

An a-like OS, an nc-OS, and a CAAC-OS are prepared as samples. Each ofthe samples is an In—Ga—Zn oxide.

First, a high-resolution cross-sectional TEM image of each sample isobtained. The high-resolution cross-sectional TEM images show that allthe samples have crystal parts.

It is known that a unit cell of an InGaZnO₄ crystal has a structure inwhich nine layers including three In—O layers and six Ga—Zn—O layers arestacked in the c-axis direction. The distance between the adjacentlayers is equivalent to the lattice spacing on the (009) plane (alsoreferred to as d value). The value is calculated to be 0.29 nm fromcrystal structural analysis. Accordingly, a portion where the latticespacing between lattice fringes is greater than or equal to 0.28 nm andless than or equal to 0.30 nm is regarded as a crystal part of InGaZnO₄.Each of lattice fringes corresponds to the a-b plane of the InGaZnO₄crystal.

FIG. 6 shows change in the average size of crystal parts (at 22 pointsto 30 points) in each sample. Note that the crystal part sizecorresponds to the length of a lattice fringe. FIG. 6 indicates that thecrystal part size in the a-like OS increases with an increase in thecumulative electron dose in obtaining TEM images, for example. As shownin FIG. 6 , a crystal part of approximately 1.2 nm (also referred to asan initial nucleus) at the start of TEM observation grows to a size ofapproximately 1.9 nm at a cumulative electron (e) dose of 4.2×10⁸e⁻/nm². In contrast, the crystal part size in the nc-OS and the CAAC-OSshows little change from the start of electron irradiation to acumulative electron dose of 4.2×10⁸ e⁻/nm². As shown in FIG. 6 , thecrystal part sizes in an nc-OS and a CAAC-OS are approximately 1.3 nmand approximately 1.8 nm, respectively, regardless of the cumulativeelectron dose. For the electron beam irradiation and TEM observation, aHitachi H-9000NAR transmission electron microscope was used. Theconditions of electron beam irradiation were as follows: theaccelerating voltage was 300 kV; the current density was 6.7×10⁵e⁻/(nm²·s); and the diameter of irradiation region was 230 nm.

In this manner, growth of the crystal part in the a-like OS is inducedby electron irradiation. In contrast, in the nc-OS and the CAAC-OS,growth of the crystal part is hardly induced by electron irradiation.Therefore, the a-like OS has an unstable structure as compared with thenc-OS and the CAAC-OS.

The a-like OS has a lower density than the nc-OS and the CAAC-OS becauseit includes a void. Specifically, the density of the a-like OS is higherthan or equal to 78.6% and lower than 92.3% of the density of the singlecrystal oxide semiconductor having the same composition. The density ofeach of the nc-OS and the CAAC-OS is higher than or equal to 92.3% andlower than 100% of the density of the single crystal oxide semiconductorhaving the same composition. Note that it is difficult to deposit anoxide semiconductor having a density of lower than 78% of the density ofthe single crystal oxide semiconductor.

For example, in the case of an oxide semiconductor having an atomicratio of In:Ga:Zn=1:1:1, the density of single crystal InGaZnO₄ with arhombohedral crystal structure is 6.357 g/cm³. Accordingly, in the caseof the oxide semiconductor having an atomic ratio of In:Ga:Zn=1:1:1, thedensity of the a-like OS is higher than or equal to 5.0 g/cm³ and lowerthan 5.9 g/cm³. For example, in the case of the oxide semiconductorhaving an atomic ratio of In:Ga:Zn=1:1:1, the density of each of thenc-OS and the CAAC-OS is higher than or equal to 5.9 g/cm³ and lowerthan 6.3 g/cm³.

Note that in the case where an oxide semiconductor having a certaincomposition does not exist in a single crystal structure, single crystaloxide semiconductors with different compositions are combined at anadequate ratio, which makes it possible to calculate density equivalentto that of a single crystal oxide semiconductor with the desiredcomposition. The density of a single crystal oxide semiconductor havingthe desired composition can be calculated using a weighted averageaccording to the combination ratio of the single crystal oxidesemiconductors with different compositions. Note that it is preferableto use as few kinds of single crystal oxide semiconductors as possibleto calculate the density.

As described above, oxide semiconductors have various structures andvarious properties. Note that an oxide semiconductor may be a stackedfilm including two or more of an amorphous oxide semiconductor, ana-like OS, an nc-OS, and a CAAC-OS, for example.

<Substrate, Insulator, Conductor>

Components other than the semiconductor of the transistor 10 aredescribed in detail below.

As the substrate 100, an insulator substrate, a semiconductor substrate,or a conductor substrate may be used, for example. As the insulatorsubstrate, a glass substrate, a quartz substrate, a sapphire substrate,a stabilized zirconia substrate (e.g., an yttria-stabilized zirconiasubstrate), or a resin substrate is used, for example. As thesemiconductor substrate, a single material semiconductor substrateformed using silicon, germanium, or the like or a semiconductorsubstrate formed using silicon carbide, silicon germanium, galliumarsenide, indium phosphide, zinc oxide, gallium oxide, or the like isused, for example. A semiconductor substrate in which an insulatorregion is provided in the above semiconductor substrate, e.g., a siliconon insulator (SOI) substrate or the like is used. As the conductorsubstrate, a graphite substrate, a metal substrate, an alloy substrate,a conductive resin substrate, or the like is used. A substrate includinga metal nitride, a substrate including a metal oxide, or the like isused. An insulator substrate provided with a conductor or asemiconductor, a semiconductor substrate provided with a conductor or aninsulator, a conductor substrate provided with a semiconductor or aninsulator, or the like is used. Alternatively, any of these substratesover which an element is provided may be used. As the element providedover the substrate, a capacitor, a resistor, a switching element, alight-emitting element, a memory element, or the like is used.

Alternatively, a flexible substrate resistant to heat treatmentperformed in manufacture of the transistor may be used as the substrate100. As a method for providing the transistor over a flexible substrate,there is a method in which the transistor is formed over a non-flexiblesubstrate and then the transistor is separated and transferred to thesubstrate 100 which is a flexible substrate. In that case, a separationlayer is preferably provided between the non-flexible substrate and thetransistor. As the substrate 100, a sheet, a film, or a foil containinga fiber may be used. The substrate 100 may have elasticity. Thesubstrate 100 may have a property of returning to its original shapewhen bending or pulling is stopped. Alternatively, the substrate 100 mayhave a property of not returning to its original shape. The thickness ofthe substrate 100 is, for example, greater than or equal to 5 μm andless than or equal to 700 μm, preferably greater than or equal to 10 μmand less than or equal to 500 μm, and further preferably greater than orequal to 15 μm and less than or equal to 300 μm. When the substrate 100has a small thickness, the weight of the semiconductor device can bereduced. When the substrate 100 has a small thickness, even in the caseof using glass or the like, the substrate 100 may have elasticity or aproperty of returning to its original shape when bending or pulling isstopped. Therefore, an impact applied to the semiconductor device overthe substrate 100, which is caused by dropping or the like, can bereduced. That is, a durable semiconductor device can be provided.

For the substrate 100 which is a flexible substrate, metal, an alloy,resin, glass, or fiber thereof can be used, for example. The flexiblesubstrate 100 preferably has a lower coefficient of linear expansionbecause deformation due to an environment is suppressed. The flexiblesubstrate 100 is formed using, for example, a material whose coefficientof linear expansion is lower than or equal to 1×10⁻³/K, lower than orequal to 5×10⁻⁵/K, or lower than or equal to 1×10⁻⁵/K. Examples of theresin include polyester, polyolefin, polyamide (e.g., nylon or aramid),polyimide, polycarbonate, and acrylic. In particular, aramid ispreferably used for the flexible substrate 100 because of its lowcoefficient of linear expansion.

As the insulator 101, an insulator having a function of blockinghydrogen or water is used. Hydrogen or water in the insulator providednear the insulator 106 a, the semiconductor 106 b, and the insulator 106c is one of the factors of carrier generation in the insulator 106 a,the semiconductor 106 b, and the insulator 106 c which also function asoxide semiconductors. Because of this, the reliability of the transistor10 might be decreased. When a substrate provided with a silicon-basedsemiconductor element such as a switching element is used as thesubstrate 100, hydrogen might be used to terminate a dangling bond inthe semiconductor element and then be diffused into the transistor 10.However, if such a structure includes the insulator 101 having afunction of blocking hydrogen or water, diffusion of hydrogen or waterfrom below the transistor 10 can be inhibited, leading to an improvementin the reliability of the transistor 10. It is preferable that theinsulator 101 be less permeable to hydrogen or water than the insulator105 and the insulator 104.

The insulator 101 preferably has a function of blocking oxygen. Ifoxygen diffused from the insulator 104 can be blocked by the insulator101, oxygen can be effectively supplied from the insulator 104 to theinsulator 106 a, the semiconductor 106 b, and the insulator 106 c.

The insulator 101 can be formed using, for example, aluminum oxide,aluminum oxynitride, gallium oxide, gallium oxynitride, yttrium oxide,yttrium oxynitride, hafnium oxide, or hafnium oxynitride. The use ofsuch a material enables the insulator 101 to function as an insulatingfilm blocking diffusion of oxygen, hydrogen, or water. The insulator 101can be formed using, for example, silicon nitride or silicon nitrideoxide. The use of such a material enables the insulator 101 to functionas an insulating film blocking diffusion of hydrogen or water. Note thatsilicon nitride oxide means a substance that contains more nitrogen thanoxygen and silicon oxynitride means a substance that contains moreoxygen than nitrogen in this specification and the like. Note thatsilicon nitride oxide means a substance that contains more nitrogen thanoxygen and silicon oxynitride means a substance that contains moreoxygen than nitrogen in this specification and the like.

At least part of the conductor 102 preferably overlaps with thesemiconductor 106 b in a region positioned between the conductor 108 aand the conductor 108 b. The conductor 102 functions as a back gate ofthe transistor 10. The conductor 102 can control the threshold voltageof the transistor 10. Control of the threshold voltage can prevent thetransistor 10 from being turned on when voltage applied to the gate(conductor 114) of the transistor 10 is low, e.g., 0 V or lower. Thus,the electrical characteristics of the transistor 10 can be easily madenormally-off characteristics.

The conductor 102 may be formed to have a single-layer structure or astacked-layer structure using a conductor containing, for example, oneor more of boron, nitrogen, oxygen, fluorine, silicon, phosphorus,aluminum, titanium, chromium, manganese, cobalt, nickel, copper, zinc,gallium, yttrium, zirconium, molybdenum, ruthenium, silver, indium, tin,tantalum, and tungsten. An alloy or a compound of the above element maybe used, for example, and a conductor containing aluminum, a conductorcontaining copper and titanium, a conductor containing copper andmanganese, a conductor containing indium, tin, and oxygen, a conductorcontaining titanium and nitrogen, or the like may be used.

The insulator 105 is provided to cover the conductor 102. An insulatorsimilar to the insulator 104 or the insulator 112 to be described latercan be used as the insulator 105.

The insulator 103 is provided to cover the insulator 105. The insulator103 preferably has a function of blocking oxygen. Providing theinsulator 103 can prevent extraction of oxygen from the insulator 104 bythe conductor 102. Accordingly, oxygen can be effectively supplied fromthe insulator 104 to the insulator 106 a, the semiconductor 106 b, andthe insulator 106 c. By improving the coverage with the insulator 103,extraction of oxygen from the insulator 104 can be further reduced andoxygen can be more effectively supplied from the insulator 104 to theinsulator 106 a, the semiconductor 106 b, and the insulator 106 c.

As the insulator 103, an oxide or a nitride containing boron, aluminum,silicon, scandium, titanium, gallium, yttrium, zirconium, indium,lanthanum, cerium, neodymium, hafnium, or thallium is used. It ispreferable to use hafnium oxide or aluminum oxide.

Of the insulators 105, 103, and 104, the insulator 103 preferablyincludes an electron trap region. When the insulators 105 and 104 have afunction of inhibiting release of electrons, the electrons trapped inthe insulator 103 behave as if they are negative fixed charges.Therefore, the threshold voltage of the transistor 10 can be changed byinjection of electrons into the insulator 103. The injection ofelectrons into the insulator 103 can be performed by applying a positiveor negative potential to the conductor 102.

Since the amount of electron injection can be controlled by the timeduring which potential is applied to the conductor 102 and/or the valueof applied potential, a desirable threshold voltage of the transistorcan be obtained. The potential applied to the conductor 102 is set suchthat a tunneling current flows through the insulator 105. For example,the applied potential is higher than or equal to 20 V and lower than orequal to 60 V, preferably higher than or equal to 24 V and lower than orequal to 50 V, more preferably higher than or equal to 30 V and lowerthan or equal to 45 V. The time during which potential is applied is,for example, longer than or equal to 0.1 seconds and shorter than orequal to 20 seconds, preferably longer than or equal to 0.2 seconds andshorter than or equal to 10 seconds.

The amounts of hydrogen and water contained in the insulator 103 arepreferably small. For example, the number of water molecules releasedfrom the insulator 103 is preferably greater than or equal to 1.0×10¹³molecules/cm² and less than or equal to 1.0×10¹⁶ molecules/cm², morepreferably greater than or equal to 1.0×10¹³ molecules/cm² and less thanor equal to 3.0×10¹⁵ molecules/cm² in thermal desorption spectroscopy(TDS) analysis in the range of surface temperatures from 100° C. to 700°C. or from 100° C. to 500° C. The details of the method for measuringthe number of released molecules using TDS analysis will be describedlater.

The amounts of hydrogen and water contained in the insulator 104 arepreferably small. The insulator 104 preferably contains excess oxygen.For example, the insulator 104 may be formed to have a single-layerstructure or a stacked-layer structure including an insulator containingboron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon,phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium,lanthanum, neodymium, hafnium, or tantalum. For example, aluminum oxide,magnesium oxide, silicon oxide, silicon oxynitride, silicon nitrideoxide, silicon nitride, gallium oxide, germanium oxide, yttrium oxide,zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, ortantalum oxide may be used for the insulator 104. Preferably, siliconoxide or silicon oxynitride is used.

The amounts of hydrogen and water contained in the insulator 104 arepreferably small. For example, the number of water molecules releasedfrom the insulator 104 is preferably greater than or equal to 1.0×10¹³molecules/cm² and less than or equal to 1.4×10¹⁶ molecules/cm², morepreferably greater than or equal to 1.0×10¹³ molecules/cm² and less thanor equal to 4.0×10¹⁵ molecules/cm², further more preferably greater thanor equal to 1.0×10¹³ molecules/cm² and less than or equal to 2.0×10¹⁵molecules/cm² in TDS analysis in the range of surface temperatures from100° C. to 700° C. or from 100° C. to 500° C. The number of hydrogenmolecules released from the insulator 104 is preferably greater than orequal to 1.0×10¹³ molecules/cm² and less than or equal to 1.2×10¹⁵molecules/cm², more preferably greater than or equal to 1.0×10¹³molecules/cm² and less than or equal to 9.0×10¹⁴ molecules/cm² in TDSanalysis in the range of surface temperatures from 100° C. to 700° C. orfrom 100° C. to 500° C. The details of the method for measuring thenumber of released molecules using TDS analysis will be described later.

As described above, impurities such as water and hydrogen form defectstates in the insulator 106 a and the insulator 106 c, and particularlyin the semiconductor 106 b, which causes a change in electricalcharacteristics of the transistor. Accordingly, by reducing the amountsof water and hydrogen contained in the insulator 104 under the insulator106 a, the semiconductor 106 b, and the insulator 106 c, formation ofdefect states formed by supply of water, hydrogen, and the like from theinsulator 104 to the semiconductor 106 b can be suppressed. The use ofsuch an oxide semiconductor with a reduced density of defect statesmakes it possible to provide a transistor with stable electricalcharacteristics.

Although the details will be described later, heat treatment needs to beperformed for dehydration, dehydrogenation, or oxygen vacancy reductionin the insulator 104, the insulator 106 a, the semiconductor 106 b, theinsulator 106 c, and the like. However, high-temperature heat treatmentmight degrade layers under the insulator 104. Specifically, in the casewhere the transistor 10 in this embodiment is stacked over asemiconductor element layer in which a semiconductor (e.g., silicon)different from the semiconductor 106 b is an active layer, the heattreatment might damage or degrade elements, wirings, and the likeincluded in the semiconductor element layer.

For example, in the case where the semiconductor element layer is formedover a silicon substrate, elements need to be reduced in resistance forminiaturization of the elements. To reduce the resistance, for example,a Cu wiring with low resistivity may be used for a wiring material, ornickel silicide may be provided in a source region and a drain region ofthe transistor to form the regions. On the other hand, a Cu wiring andnickel silicide have low heat resistance. For example, high-temperatureheat treatment on a Cu wiring causes formation of a void or hillock orCu diffusion. High-temperature heat treatment on nickel silicide expandsthe silicide region so that the source region and the drain region ofthe transistor are short-circuited.

Thus, the above-described heat treatment needs to be performed in atemperature range that does not degrade the semiconductor element layerin a lower layer. However, in the case where the insulator 104 containsmuch water and hydrogen at the time of being formed, such heat treatmentin a temperature range that does not degrade the semiconductor elementlayer in the lower layer cannot remove the water, hydrogen, and the likesufficiently from the insulator 104 in some cases. Moreover, if heattreatment in such a temperature range is performed after formation ofthe insulator 106 a, the semiconductor 106 b, and the insulator 106 c,water, hydrogen, and the like are supplied from the insulator 104 to thesemiconductor 106 b and the like, forming defect states.

In contrast, water, hydrogen, and the like can be sufficientlyeliminated from the insulator 104 of this embodiment by heating at arelatively low temperature (e.g., in the range higher than or equal to350° C. and lower than or equal to 445° C.) because the amounts of waterand hydrogen contained in the insulator 104 of this embodiment are smallas described above. Moreover, even in the case where heat treatmentwithin the similar temperature range is performed after the formation ofthe insulator 106 a, the semiconductor 106 b, and the insulator 106 c,formation of defect states in the semiconductor 106 b and the like canbe suppressed because of the sufficiently small amounts of water andhydrogen in the insulator 104.

The insulator 104 is preferably formed by a PECVD method because ahigh-quality film can be obtained at a relatively low temperature.However, in the case where a silicon oxide film, for example, is formedby a PECVD method, silicon hydride or the like is often used as a sourcegas, and as a result, hydrogen, water, or the like enters the insulator104 during the formation of the insulator 104. For this reason, asilicon halide is preferably used as the source gas for the formation ofthe insulator 104 of this embodiment. As the silicon halide, forexample, silicon tetrafluoride (SiF₄), silicon tetrachloride (SiCl₄),silicon trichloride (SiHCl₃), dichlorosilane (SiH₂Cl₂), or silicontetrabromide (SiBr₄) can be used.

When a silicon halide is used as the source gas for the formation of theinsulator 104, halogen is sometimes contained in the insulator 104. Inaddition, a constituent of the insulator 104 and halogen might form acovalent bond. For example, in the case where the insulator 104 isformed using SiF₄ as the source gas, fluorine is sometimes contained inthe insulator 104 and a Si—F covalent bond might be formed. Theinsulator 104 having a Si—F covalent bond exhibits a spectrum peak inthe range from 685.4 eV to 687.5 eV when analyzed by X-ray photoelectronspectroscopy (XPS) in some cases.

When a silicon halide is used as the source gas for the formation of theinsulator 104, a silicon hydride may be used in addition to the siliconhalide. In that case, the amounts of hydrogen and water in the insulator104 can be reduced as compared with the case where only a siliconhydride is used as the source gas, and the deposition rate can beimproved as compared with the case where only a silicon halide is usedas the source gas. For example, SiF₄ and SiH₄ may be used as the sourcegas for the formation of the insulator 104. Note that the flow ratio ofSiF₄ to SiH₄ may be determined as appropriate in view of the amounts ofwater and hydrogen in the insulator 104 and the deposition rate. Thedetails of the method for forming the insulator 104 will be describedlater.

Not only the amounts of water and hydrogen contained in the insulator104, but also the amounts of water and hydrogen contained in a stackedfilm of insulators (in this embodiment, a stacked film of the insulator105, the insulator 103, and the insulator 104) provided between theinsulator 101 and the insulator 106 a are preferably small. When theinsulator 101 has a function of blocking water and hydrogen as describedabove, water and hydrogen supplied to an oxide to be the insulator 106 aor the semiconductor 106 b while the oxide is being deposited are thosecontained in the insulator 105, the insulator 103, and the insulator104. Accordingly, when the amounts of water and hydrogen contained inthe stacked film of the insulator 105, the insulator 103, and theinsulator 104 are sufficiently small at the time of deposition for theoxide to be the insulator 106 a or the semiconductor 106 b, the amountsof water and hydrogen supplied to the insulator 106 a and thesemiconductor 106 b can be small.

The amounts of hydrogen and water contained in the stacked film of theinsulator 105, the insulator 103, and the insulator 104 are preferablysmall. For example, the number of water molecules released from theinsulator 104 is preferably greater than or equal to 1.0×10¹³molecules/cm² and less than or equal to 1.4×10¹⁶ molecules/cm², morepreferably greater than or equal to 1.0×10¹³ molecules/cm² and less thanor equal to 4.0×10¹⁵ molecules/cm², further more preferably greater thanor equal to 1.0×10¹³ molecules/cm² and less than or equal to 2.0×10¹⁵molecules/cm² in TDS analysis in the range of surface temperatures from100° C. to 700° C. or from 100° C. to 500° C. The number of hydrogenmolecules released from the insulator 104 is preferably greater than orequal to 1.0×10¹³ molecules/cm² and less than or equal to 1.2×10¹⁵molecules/cm², more preferably greater than or equal to 1.0×10¹³molecules/cm² and less than or equal to 9.0×10¹⁴ molecules/cm² in TDSanalysis in the range of surface temperatures from 100° C. to 700° C. orfrom 100° C. to 500° C. The details of the method for measuring thenumber of released molecules using TDS analysis will be described later.

Such an insulator in which water and hydrogen are small may be used asan insulator other than the insulator 104, such as the insulator 105, orthe insulator 112 or an insulator 118 to be described later.Furthermore, such an insulator may be used as the insulator 101, theinsulator 116, or the like as long as the insulator has an adequateblocking property against hydrogen or water. In the case where asemiconductor element layer, a wiring layer, or the like is providedunder the insulator 101, the insulator may be used for an interlayerinsulating film between the insulator 101 and the semiconductor elementlayer or the wiring layer. In the case where a semiconductor elementlayer, a wiring layer, or the like is provided over the insulator 118,the insulator may be used for an interlayer insulating film between theinsulator 118 and the semiconductor element layer or the wiring layer.

The insulator 104 is preferably an insulator containing excess oxygen.Such insulator 104 makes it possible to supply oxygen from the insulator104 to the insulator 106 a, the semiconductor 106 b, and the insulator106 c. The supplied oxygen can reduce oxygen vacancies which are to bedefects in the insulator 106 a, the semiconductor 106 b, and theinsulator 106 c which are oxide semiconductors. As a result, theinsulator 106 a, the semiconductor 106 b, and the insulator 106 c can beoxide semiconductors with a low density of defect states and stablecharacteristics.

In this specification and the like, excess oxygen refers to oxygen inexcess of the stoichiometric composition, for example. Alternatively,excess oxygen refers to oxygen released from a film or layer containingexcess oxygen by heating, for example. Excess oxygen can move inside afilm or a layer. Excess oxygen moves between atoms in a film or a layer,or replaces oxygen that is a constituent of a film or a layer and moveslike a billiard ball, for example.

The insulator 104 containing excess oxygen releases oxygen molecules,the number of which is greater than or equal to 1.0×10¹⁴ molecules/cm²and less than or equal to 1.0×10¹⁶ molecules/cm² and preferably greaterthan or equal to 1.0×10¹⁵ molecules/cm² and less than or equal to5.0×10¹⁵ molecules/cm² in TDS analysis in the range of a surfacetemperature from 100° C. to 700° C. or from 100° C. to 500° C.

A method for measuring the amount of released molecules using TDSanalysis is described below by taking the amount of released oxygen asan example.

The total amount of gas released from a measurement sample in TDSanalysis is proportional to the integral value of the ion intensity ofthe released gas. Then, comparison with a reference sample is made,whereby the total amount of released gas can be calculated.

For example, the number of oxygen molecules (N_(O2)) released from ameasurement sample can be calculated according to the following formulausing the TDS results of a silicon substrate containing hydrogen at apredetermined density, which is a reference sample, and the TDS resultsof the measurement sample. Here, all gases having a mass-to-charge ratioof 32 which are obtained in the TDS analysis are assumed to originatefrom an oxygen molecule. Note that CH₃OH, which is a gas having themass-to-charge ratio of 32, is not taken into consideration because itis unlikely to be present. Furthermore, an oxygen molecule including anoxygen atom having a mass number of 17 or 18 which is an isotope of anoxygen atom is not taken into consideration either because theproportion of such a molecule in the natural world is negligible.N_(O2)=N_(H2)/S_(H2)×S_(O2)×α

The value N_(H2) is obtained by conversion of the number of hydrogenmolecules desorbed from the standard sample into densities. The valueS_(H2) is the integral value of ion intensity when the standard sampleis subjected to the TDS analysis. Here, the reference value of thestandard sample is set to N_(H2)/S_(H2). S_(O2) is the integral value ofion intensity when the measurement sample is analyzed by TDS. The valuea is a coefficient affecting the ion intensity in the TDS analysis.Refer to Japanese Published Patent Application No. H6-275697 for detailsof the above formula. The amount of released oxygen was measured with athermal desorption spectroscopy apparatus produced by ESCO Ltd.,EMD-WA1000S/W, using a silicon substrate containing a certain amount ofhydrogen atoms as the reference sample.

Furthermore, in the TDS analysis, oxygen is partly detected as an oxygenatom. The ratio of oxygen molecules to oxygen atoms can be calculatedfrom the ionization rate of the oxygen molecules. Note that since theabove a includes the ionization rate of the oxygen molecules, the numberof the released oxygen atoms can also be estimated through themeasurement of the number of the released oxygen molecules.

Note that N_(O2) is the number of the released oxygen molecules. Thenumber of released oxygen in the case of being converted into oxygenatoms is twice the number of the released oxygen molecules.

Furthermore, the insulator from which oxygen is released by heattreatment may contain a peroxide radical. Specifically, the spin densityattributed to the peroxide radical is greater than or equal to 5×10¹⁷spins/cm³. Note that the insulator containing a peroxide radical mayhave an asymmetric signal with a g factor of approximately 2.01 inelectron spin resonance (ESR).

The insulator 104 may have a function of preventing diffusion ofimpurities from the substrate 100.

As described above, the top surface or the bottom surface of thesemiconductor 106 b preferably has high planarity. Thus, to improve theplanarity, the top surface of the insulator 104 may be subjected toplanarization treatment performed by a chemical mechanical polishing(CMP) method or the like.

The conductors 108 a and 108 b serve as a source electrode and a drainelectrode of the transistor 10.

The conductors 108 a and 108 b may be formed to have a single-layerstructure or a stacked-layer structure using a conductor containing, forexample, one or more of boron, nitrogen, oxygen, fluorine, silicon,phosphorus, aluminum, titanium, chromium, manganese, cobalt, nickel,copper, zinc, gallium, yttrium, zirconium, molybdenum, ruthenium,silver, indium, tin, tantalum, and tungsten. An alloy or a compound ofthe above element may be used, for example, and a conductor containingaluminum, a conductor containing copper and titanium, a conductorcontaining copper and manganese, a conductor containing indium, tin, andoxygen, a conductor containing titanium and nitrogen, or the like may beused.

Here, it is preferable that the bottom surfaces of the conductors 108 aand 108 b not be in contact with the top surface of the insulator 104.For example, as in FIG. 1B, bottom surfaces of the conductors 108 a and108 b may be in contact with only a top surface of the semiconductor 106b. This structure can inhibit extraction of oxygen from the insulator104 at the bottom surfaces of the conductors 108 a and 108 b.Accordingly, the conductors 108 a and 108 b can be prevented from beingpartly oxidized to have increased resistivity, and oxygen can beeffectively supplied from the insulator 104 to the insulator 106 a, thesemiconductor 106 b, and the insulator 106 c.

At least part of the conductors 108 a and 108 b preferably overlaps withthe insulator 112 with the insulator 106 c provided therebetween in aregion not overlapping with the conductor 114. For example, theinsulator 106 c covers most of the top surfaces of the conductors 108 aand 108 b as illustrated in FIG. 1B. This structure can inhibitextraction of oxygen from the insulator 112 at the top surfaces of theconductors 108 a and 108 b. Accordingly, the conductors 108 a and 108 bcan be prevented from being partly oxidized to have increasedresistivity, and oxygen can be effectively supplied from the insulator112 to the insulator 106 a, the semiconductor 106 b, and the insulator106 c.

The insulator 112 functions as a gate insulating film of the transistor10. Like the insulator 104, the insulator 112 may be an insulatorcontaining excess oxygen. Such insulator 112 makes it possible to supplyoxygen from the insulator 112 to the insulator 106 a, the semiconductor106 b, and the insulator 106 c.

The insulator 112 may be formed to have a single-layer structure or astacked-layer structure including an insulator containing, for example,boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon,phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium,lanthanum, neodymium, hafnium, or tantalum. The insulator 112 may beformed using, for example, aluminum oxide, magnesium oxide, siliconoxide, silicon oxynitride, silicon nitride oxide, silicon nitride,gallium oxide, germanium oxide, yttrium oxide, zirconium oxide,lanthanum oxide, neodymium oxide, hafnium oxide, or tantalum oxide.

The conductor 114 functions as a gate electrode of the transistor 10.The conductor 114 can be formed using the conductor that can be used asthe conductor 102.

Here, as illustrated in FIG. 1C, the semiconductor 106 b can beelectrically surrounded by an electric field of the conductor 102 andthe conductor 114 (a structure in which a semiconductor is electricallysurrounded by an electric field of a conductor is referred to as asurrounded channel (s-channel) structure). Therefore, a channel isformed in the entire semiconductor 106 b (the top, bottom, and sidesurfaces). In the s-channel structure, a large amount of current canflow between a source and a drain of a transistor, so that a highon-state current can be obtained.

In the case where the transistor has the s-channel structure, a channelis formed also in the side surface of the semiconductor 106 b.Therefore, as the semiconductor 106 b has a larger thickness, thechannel region becomes larger. In other words, the thicker thesemiconductor 106 b is, the larger the on-state current of thetransistor is. In addition, when the semiconductor 106 b is thicker, theproportion of the region with a high carrier controllability increases,leading to a smaller subthreshold swing value. For example, thesemiconductor 106 b has a region with a thickness greater than or equalto 10 nm, preferably greater than or equal to 20 nm, further preferablygreater than or equal to 30 nm, still further preferably greater than orequal to 50 nm. Since the productivity of the semiconductor device mightbe decreased, the semiconductor 106 b has a region with a thickness of,for example, less than or equal to 300 nm, preferably less than or equalto 200 nm, further preferably less than or equal to 150 nm.

The s-channel structure is suitable for a miniaturized transistorbecause a high on-state current can be achieved. A semiconductor deviceincluding the miniaturized transistor can have a high integration degreeand high density. For example, the transistor includes a region having achannel length of preferably less than or equal to 40 nm, furtherpreferably less than or equal to 30 nm, still further preferably lessthan or equal to 20 nm and a region having a channel width of preferablyless than or equal to 40 nm, further preferably less than or equal to 30nm, still further preferably less than or equal to 20 nm.

The insulator 116 functions as a protective insulating film of thetransistor 10. Here, the thickness of the insulator 116 can be greaterthan or equal to 5 nm, or greater than or equal to 20 nm, for example.It is preferable that at least part of the insulator 116 be in contactwith the top surface of the insulator 104 or a top surface of theinsulator 112.

The insulator 116 may be formed to have a single-layer structure or astacked-layer structure including an insulator containing, for example,carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon,phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium,lanthanum, neodymium, hafnium, or tantalum. The insulator 116 preferablyhas a blocking effect against oxygen, hydrogen, water, alkali metal,alkaline earth metal, and the like. As such an insulator, for example, anitride insulating film can be used. As examples of the nitrideinsulating film, a silicon nitride film, a silicon nitride oxide film,an aluminum nitride film, an aluminum nitride oxide film, and the likecan be given. Note that instead of the nitride insulating film, an oxideinsulating film having a blocking effect against oxygen, hydrogen,water, and the like, may be provided. As examples of the oxideinsulating film, an aluminum oxide film, an aluminum oxynitride film, agallium oxide film, a gallium oxynitride film, an yttrium oxide film, anyttrium oxynitride film, a hafnium oxide film, a hafnium oxynitridefilm, and the like can be given.

Here, it is preferable that the insulator 116 be formed by a sputteringmethod and it is further preferable that the insulator 116 be formed bya sputtering method in an atmosphere containing oxygen. When theinsulator 116 is formed by a sputtering method, oxygen is added to thevicinity of a surface of the insulator 104 or a surface of the insulator112 (after the formation of the insulator 116, an interface between theinsulator 116 and the insulator 104 or the insulator 112) at the sametime as the formation.

It is preferable that the insulator 116 be less permeable to oxygen thanthe insulator 104 and the insulator 112 and have a function of blockingoxygen. Providing the insulator 116 can prevent oxygen from beingexternally released to above the insulator 116 at the time of supply ofoxygen from the insulator 104 and the insulator 112 to the insulator 106a, the semiconductor 106 b, and the insulator 106 c.

Aluminum oxide is preferably used as the insulator 116 because it ishighly effective in preventing transmission of both oxygen andimpurities such as hydrogen and moisture.

An oxide that can be used for the insulator 106 a or the insulator 106 ccan be used for the insulator 116. Such an oxide can be relativelyeasily formed by a sputtering method, and thus, oxygen can beeffectively added to the insulator 104 and the insulator 112. Theinsulator 116 is preferably formed with an oxide insulator containingIn, such as an In—Al oxide, an In—Ga oxide, or an In—Ga—Zn oxide. Anoxide insulator containing In is favorably used for the insulator 116because the number of particles generated at the time of the depositionby a sputtering method is small.

The insulator 118 functions as an interlayer insulating film. Theinsulator 118 may be formed using the insulator that can be used as theinsulator 105.

The conductor 120 a and the conductor 120 b function as wiringselectrically connected to the source electrode and the drain electrodeof the transistor 10. As the conductor 120 a and the conductor 120 b,the conductor that can be used for the conductor 108 a and the conductor108 b is used.

When the above-described structure is employed, a transistor with stableelectrical characteristics, a transistor having a low leakage current inan off state, a transistor with high frequency characteristics, atransistor with normally-off electrical characteristics, a transistorwith a small subthreshold swing value, or a highly reliable transistorcan be provided.

<Modification Example of Transistor>

Modification examples of the transistor 10 are described below withreference to FIGS. 7A to 7D to FIGS. 12A to 12D. FIGS. 7A to 7D to FIGS.12A to 12D are cross-sectional views in the channel length direction andthose in the channel width direction like FIGS. 1B and 1C.

A transistor 12 illustrated in FIGS. 7A and 7B differs from thetransistor 10 in that the insulator 105 is not provided. That is, theconductor 102 is surrounded by the insulator 101 and the insulator 103.Here, the insulator 101 and the insulator 103 preferably have anoxygen-blocking property. This structure can inhibit oxidation of theconductor 102 due to extraction of oxygen from the conductor 102 by theinsulator 104 and the like. Accordingly, the conductor 102 can beprevented from being partly oxidized to have increased resistivity, andoxygen can be effectively supplied to the insulator 106 a, thesemiconductor 106 b, and the insulator 106 c.

A transistor 14 illustrated in FIGS. 7C and 7D differs from thetransistor 10 in that the insulator 103 and the insulator 105 are notprovided. That is, the conductor 102 is covered with the insulator 104.Here, the insulator 101 preferably has an oxygen-blocking property. Thisstructure can prevent oxygen diffused in the insulator 104 from beingdiffused into layers under the insulator 104 when oxygen is suppliedfrom the insulator 104 to the insulator 106 a, the semiconductor 106 b,and the insulator 106 c. Accordingly, oxygen can be effectively suppliedto the insulator 106 a, the semiconductor 106 b, and the insulator 106c.

A highly oxidation-resistant conductor such as Ru, titanium nitride,tungsten silicide, platinum, iridium, ruthenium oxide, or iridium oxidemay be used for the conductor 102 in the transistor 14. With thisstructure, the conductor 102 has resistance to oxidation by halogen suchas fluorine contained in a deposition atmosphere for the insulator 104,so that oxidation of the conductor 102 can be prevented.

A transistor 16 illustrated in FIGS. 8A and 8B differs from thetransistor 10 in that the conductor 102, the insulator 103, and theinsulator 105 are not provided. Here, the insulator 101 preferably hasan oxygen-blocking property. This structure can prevent oxygen diffusedin the insulator 104 from being diffused into layers under the insulator104 when oxygen is supplied from the insulator 104 to the insulator 106a, the semiconductor 106 b, and the insulator 106 c. Accordingly, oxygencan be effectively supplied to the insulator 106 a, the semiconductor106 b, and the insulator 106 c.

A transistor 18 illustrated in FIGS. 8C and 8D differs from thetransistor 14 in that a stacked structure in which a conductor 102 b isformed over a conductor 102 a is employed instead of the conductor 102.The conductor 102 a may be formed with the conductor that can be used asthe conductor 102. The conductor 102 b may be formed with a highlyoxidation-resistant conductor such as Ru, titanium nitride, tungstensilicide, platinum, iridium, ruthenium oxide, or iridium oxide. Withthis structure, the conductor 102 b has resistance to oxidation byhalogen such as fluorine contained in a deposition atmosphere for theinsulator 104, so that oxidation of the conductor 102 a can beprevented.

A transistor 20 illustrated in FIGS. 9A and 9B differs from thetransistor 10 in that an insulator 107 is provided over the insulator101 and the conductor 102 is embedded in an opening in the insulator107. The insulator 107 may be formed with the insulator that can be usedas the insulator 105. It is preferable that top surfaces of theinsulator 107 and the conductor 102 be subjected to planarizationtreatment such as a CMP method in order to improve its planarity. Withthis structure, the planarity of a surface on which the semiconductor106 b is formed is not degraded even when the conductor 102 serving as aback gate is provided. Accordingly, the carrier mobility can be improvedand the on-state current of the transistor 20 can be increased.Moreover, since there is no surface unevenness of the insulator 104caused by the shape of the conductor 102, leakage current generatedbetween the conductor 108 a or 108 b serving as a drain and theconductor 102 through an uneven portion of the insulator 104 can bereduced. Thus, the off-state current of the transistor 20 can bereduced.

A transistor 22 illustrated in FIGS. 10A and 10B differs from thetransistor 20 in that an insulator 117 is formed to cover top surfacesof the conductor 108 a, the conductor 108 b, and the insulator 104, anopening reaching the semiconductor 106 b is formed in the insulator 117,and the insulator 106 c, the insulator 112, and the conductor 114 areprovided to fill the opening. The conductor 108 a and the conductor 108b are separated by the opening. In the transistor 22, the conductor 114serving as a gate electrode is formed in a self-aligned manner byfilling the opening formed in the insulator 117 and the like; thus, thetransistor 22 can be called a trench gate self-aligned (TGSA) s-channelFET.

The insulator 117 may be formed with the insulator that can be used asthe insulator 104. A top surface of the insulator 117 is preferablyplanarized by a CMP method.

In the case where a silicon halide such as SiF₄ is used for theformation of the insulator 117 as in the formation of the insulator 104,halogen such as fluorine is contained in the insulator 117. Oxygen inthe insulator 117 is replaced with fluorine by heat treatment, so thatoxygen is released. A structure may be employed in which the releasedoxygen is supplied to the insulator 106 a or the semiconductor 106 b. Itis preferable that halogen such as fluorine be contained in theinsulator 117 and the insulator 117 function as a low-k film with arelative permittivity of lower than 3.5, preferably lower than 3. Suchan insulator used as the insulator 117 can further reduce the parasiticcapacitance.

In the transistor 22, the insulator 117, the insulator 106 c, and theinsulator 112 are provided between the conductor 108 a and the conductor114 and between the conductor 108 b and the conductor 114. Accordingly,the distance between a top surface of the conductor 108 a and a bottomsurface of the conductor 114 and the distance between a top surface ofthe conductor 108 b and the bottom surface of the conductor 114 can beincreased by the thickness of the insulator 117. Therefore, parasiticcapacitance generated in a region where the conductor 114 and theconductor 108 a or the conductor 108 b overlap each other can bereduced. The switching speed of the transistor can be improved by thereduction in parasitic capacitance, so that the transistor can have highfrequency characteristics.

A transistor 24 illustrated in FIGS. 10C and 10D differs from thetransistor 22 in that top surfaces of the insulator 117, the insulator106 c, the insulator 112, and the conductor 114 are substantiallyaligned with one another and flat. This can be achieved by planarizingthe top surfaces of the insulator 117, the insulator 106 c, theinsulator 112, and the conductor 114 by a CMP method or the like.

In this structure, there is hardly any region where the conductor 114and the conductor 108 a or the conductor 108 b overlap each other; as aresult, parasitic capacitance in the transistor 24 between a gate and asource and between the gate and a drain can be reduced. The switchingspeed of the transistor can be improved by the reduction in parasiticcapacitance, so that the transistor can have high frequencycharacteristics.

A transistor 29 illustrated in FIGS. 11A and 11B differs from thetransistor 24 in that the insulator 107 is provided over the insulator101 and the conductor 102 is embedded in an opening in the insulator107. In addition, the transistor 29 differs from the transistor 24 alsoin that the insulator 106 c covers the insulator 106 a and thesemiconductor 106 b. In the transistor 29, the insulator 106 c is notprovided on a side surface of the opening formed in the insulator 117.With this structure, the conductor 114 in the opening in the insulator117 can have a longer length in the channel length direction than theconductor 114 in the transistor 24 or the like.

In the transistor 29, a metal oxide 111 a is provided on top and sidesurfaces of the conductor 108 a and a metal oxide 111 b is provided ontop and side surfaces of the conductor 108 b. The thicknesses of themetal oxides 111 a and 111 b on the side surfaces of the conductors 108a and 108 b are larger than those on the top surfaces of the conductors108 a and 108 b in some cases. This is because the metal oxides 111 aand 111 b on the top surfaces of the conductors 108 a and 108 b areformed in a different step from a step of forming the metal oxides 111 aand 111 b on the side surfaces of the conductors 108 a and 108 b.

The conductors 108 a and 108 b are oxidized in one or more steps offormation of the insulator 117, formation of the insulator 112, plasmatreatment, and the like, whereby the metal oxides 111 a and 111 b areformed. In that case, the metal oxides 111 a and 111 b are oxides thatinclude a constituent element of the conductors 108 a and 108 b.

The total volume of the conductor 108 a and the metal oxide 111 a issometimes larger than the volume of the conductor 108 a before the metaloxide 111 a is formed. Similarly, the total volume of the conductor 108b and the metal oxide 111 b is sometimes larger than the volume of theconductor 108 b before the metal oxide 111 b is formed.

In the transistor 29 including the metal oxides 111 a and 111 b providedon the top and side surfaces of the conductors 108 a and 108 b, theelectric field concentration at an end portion of a drain electrode isrelieved. Therefore, the transistor 29 can be highly reliable and have asmall short-channel effect.

Note that formation of the metal oxides 111 a and 111 b is not limitedto the transistor 29. For example, another transistor may include themetal oxides 111 a and 111 b.

A transistor 26 illustrated in FIGS. 12A and 12B differs from thetransistor 20 in that the conductors 108 a and 108 b are not providedand side surfaces of end portions of the conductor 114 and the insulator112 are substantially aligned with each other. The above-describedtransistors such as the transistor 10 and the like are formed by agate-last method by which the low-resistance regions 109 a and 109 bserving as a source region and a drain region are formed before theconductor 114 serving as a gate is formed in the process for fabricatinga transistor. In contrast, the transistor 26 is formed by a gate-firstmethod by which the low-resistance regions 109 a and 109 b serving as asource region and a drain region are formed after the conductor 114serving as a gate is formed in the process for fabricating a transistor.

The low-resistance regions 109 a and 109 b in the transistor 26 includeat least one of elements included in the insulator 116. It is preferablethat part of the low-resistance regions 109 a and 109 b be substantiallyin contact with a region of the semiconductor 106 b overlapping with theconductor 114 (a channel formation region) or overlap with part of theregion.

Since an element included in the insulator 116 is added to thelow-resistance regions 109 a and 109 b, the concentration of theelement, which is measured by SIMS, in the low-resistance regions 109 aand 109 b is higher than that in a region of the semiconductor 106 bother than the low-resistance regions 109 a and 109 b (for example, aregion of the semiconductor 106 b overlapping with the conductor 114).

Preferable examples of the element added to the low-resistance regions109 a and 109 b are boron, magnesium, aluminum, silicon, titanium,vanadium, chromium, nickel, zinc, gallium, germanium, yttrium,zirconium, niobium, molybdenum, indium, tin, lanthanum, cerium,neodymium, hafnium, tantalum, and tungsten. These elements relativelyeasily form oxides and the oxides can serve as a semiconductor or aninsulator; therefore, these elements are suitable as an element added tothe insulator 106 a, the semiconductor 106 b, or the insulator 106 c.For example, the concentration of the element in the low-resistanceregions 109 a and 109 b is preferably higher than or equal to 1×10¹⁴molecules/cm² and lower than or equal to 2×10¹⁶ molecules/cm². Theconcentration of the element in the low-resistance regions 109 a and 109b in the insulator 106 c is higher than that in the region of thesemiconductor 106 b other than the low-resistance regions 109 a and 109b (for example, the region of the semiconductor 106 b overlapping withthe conductor 114).

Since the low-resistance regions 109 a and 109 b can become n-type bycontaining nitrogen, the concentration of nitrogen, which is measured bySIMS, in the low-resistance regions 109 a and 109 b is higher than thatin a region of the semiconductor 106 b other than the low-resistanceregions 109 a and 109 b (for example, the region of the semiconductor106 b overlapping with the conductor 114).

The formation of the low-resistance region 109 a and the low-resistanceregion 109 b leads to a reduction in contact resistance between theconductor 108 a or 108 b and the insulator 106 a, the semiconductor 106b, or the insulator 106 c, whereby the transistor 10 can have highon-state current.

In the transistor 26, the semiconductor 106 b is surrounded by theinsulator 106 a and the insulator 106 c. Thus, the insulator 106 a andthe insulator 106 c are in contact with a side surface of an end portionof the semiconductor 106 b, in particular, the vicinity of the sidesurface of the end portion in the channel width direction. With thisstructure, near the end portion of the side surface of the semiconductor106 b, continuous junction is formed between the semiconductor 106 b andthe insulator 106 a or the insulator 106 c, and the density of defectstates is reduced. Although on-state current flows more easily throughthe transistor including the low-resistance regions 109 a and 109 b, theside surface of the end portion of the semiconductor 106 b in thechannel width direction does not form parasitic channel; therefore,stable electrical characteristics can be obtained.

A transistor 28 illustrated in FIGS. 12C and 12D differs from thetransistor 10 in that the insulator 112 and the conductor 114 are notprovided. That is, the transistor 28 is what we call a bottom gatetransistor.

The structure and method described in this embodiment can be implementedby being combined as appropriate with any of the other structures andmethods described in the other embodiments.

Embodiment 2

In this embodiment, methods for manufacturing semiconductor devices ofembodiments of the present invention are described with reference toFIGS. 13A to 13H to FIGS. 19A to 19F.

<Fabrication Method of Transistor>

A method for fabricating the transistor 10 is described below withreference to FIGS. 13A to 13H, FIGS. 14A to 14F, and FIGS. 15A to 15D.

First, the substrate 100 is prepared. Any of the above-mentionedsubstrates can be used for the substrate 100.

Next, the insulator 101 is formed. Any of the above-mentioned insulatorscan be used for the insulator 101.

The insulator 101 may be formed by a sputtering method, a chemical vapordeposition (CVD) method, a molecular beam epitaxy (MBE) method, a pulsedlaser deposition (PLD) method, an atomic layer deposition (ALD) method,or the like.

Next, a conductor to be the conductor 102 is formed. Any of theabove-described conductors can be used for the conductor to be theconductor 102. The conductor can be formed by a sputtering method, a CVDmethod, an MBE method, a PLD method, an ALD method, or the like.

Next, a resist or the like is formed over the conductor and processingis performed using the resist or the like, whereby the conductor 102 isformed (see FIGS. 13A and 13B). Note that the case where the resist issimply formed also includes the case where a BARC is formed below theresist.

The resist is removed after the object is processed by etching or thelike. For the removal of the resist, plasma treatment and/or wet etchingare/is used. Note that as the plasma treatment, plasma ashing ispreferable. In the case where the removal of the resist or the like isnot enough, the remaining resist or the like may be removed using ozonewater and/or hydrofluoric acid at a concentration higher than or equalto 0.001 volume % and lower than or equal to 1 volume %, and the like.

Then, the insulator 105 is formed. Any of the above-described insulatorscan be used for the insulator 105. The insulator 105 can be formed by asputtering method, a CVD method, an MBE method, a PLD method, an ALDmethod, or the like. In order to reduce water and hydrogen contained inthe insulator 105, the insulator 105 may be formed while the substrateis being heated. For example, in the case where a semiconductor elementlayer is provided below the transistor 10, the heat treatment may beperformed in a relatively low temperature range (e.g., higher than orequal to 350° C. and lower than or equal to 445° C.).

Alternatively, the insulator 105 may be formed by a PECVD method in amanner similar to that of the insulator 104 to be described later inorder to reduce water and hydrogen contained in the insulator 105.

Then, the insulator 103 is formed. Any of the above-described insulatorscan be used for the insulator 103. The insulator 103 can be formed by asputtering method, a CVD method, an MBE method, a PLD method, an ALDmethod, or the like. In order to reduce water and hydrogen contained inthe insulator 103, the insulator 103 may be formed while the substrateis being heated. For example, in the case where a semiconductor elementlayer is provided under the transistor 10, the heat treatment may beperformed in a relatively low temperature range (e.g., higher than orequal to 350° C. and lower than or equal to 445° C.).

CVD methods can be classified into a plasma enhanced CVD (PECVD) methodusing plasma, a thermal CVD (TCVD) method using heat, a photo CVD methodusing light, and the like. Moreover, the CVD methods can be classifiedinto a metal CVD (MCVD) method and a metal organic CVD (MOCVD) methoddepending on a source gas.

In the case of a PECVD method, a high quality film can be obtained atrelatively low temperature. Furthermore, a TCVD method does not useplasma and thus causes less plasma damage to an object. For example, awiring, an electrode, an element (e.g., transistor or capacitor), or thelike included in a semiconductor device might be charged up by receivingelectric charges from plasma. In that case, accumulated electric chargesmight break the wiring, electrode, element, or the like included in thesemiconductor device. Such plasma damage is not caused in the case ofusing a TCVD method, and thus the yield of a semiconductor device can beincreased. In addition, since plasma damage does not occur in thedeposition by a TCVD method, a film with few defects can be obtained.

An ALD method also causes less plasma damage to an object. An ALD methoddoes not cause plasma damage during deposition, so that a film with fewdefects can be obtained.

Unlike in a deposition method in which particles ejected from a targetor the like are deposited, in a CVD method and an ALD method, a film isformed by reaction at a surface of an object. Thus, a CVD method and anALD method enable favorable step coverage almost regardless of the shapeof an object. In particular, an ALD method enables excellent stepcoverage and excellent thickness uniformity and can be favorably usedfor covering a surface of an opening with a high aspect ratio, forexample. For that reason, a formed film is less likely to have a pinholeor the like. On the other hand, an ALD method has a relatively lowdeposition rate; thus, it is sometimes preferable to combine an ALDmethod with another deposition method with a high deposition rate suchas a CVD method.

When a CVD method or an ALD method is used, composition of a film to beformed can be controlled with a flow rate ratio of the source gases. Forexample, by the CVD method or the ALD method, a film with a desiredcomposition can be formed by adjusting the flow ratio of a source gas.Moreover, with a CVD method or an ALD method, by changing the flow rateratio of the source gases while forming the film, a film whosecomposition is continuously changed can be formed. In the case where thefilm is formed while changing the flow rate ratio of the source gases,as compared to the case where the film is formed using a plurality ofdeposition chambers, time taken for the deposition can be reducedbecause time taken for transfer and pressure adjustment is omitted.Thus, semiconductor devices can be manufactured with improvedproductivity.

In a conventional deposition apparatus utilizing a CVD method, one or aplurality of source gases for reaction are supplied to a chamber at thesame time at the time of deposition. In a deposition apparatus utilizingan ALD method, a source gas (also called a precursor) for reaction and agas serving as a reactant are alternately introduced into a chamber, andthen the gas introduction is repeated. Note that the gases to beintroduced can be switched using the respective switching valves (alsoreferred to as high-speed valves).

For example, deposition is performed in the following manner. First, aprecursor is introduced into a chamber and adsorbed onto a substratesurface (first step). Here, the precursor is adsorbed onto the substratesurface, whereby a self-limiting mechanism of surface chemical reactionworks and no more precursor is adsorbed onto a layer of the precursorover the substrate. Note that the proper range of substrate temperaturesat which the self-limiting mechanism of surface chemical reaction worksis also referred to as an ALD window. The ALD window depends on thetemperature characteristics, vapor pressure, decomposition temperature,and the like of a precursor. Next, an inert gas (e.g., argon ornitrogen) or the like is introduced into the chamber, so that anexcessive precursor, a reaction product, and the like are released fromthe chamber (second step). Instead of introduction of an inert gas,vacuum evacuation can be performed to release an excessive precursor, areaction product, and the like from the chamber. Then, a reactant (e.g.,an oxidizer such as H₂O or O₃) is introduced into the chamber to reactwith the precursor adsorbed onto the substrate surface, whereby part ofthe precursor is removed while the molecules of the film are adsorbedonto the substrate (third step). After that, introduction of an inertgas or vacuum evacuation is performed, whereby excessive reactant, areaction product, and the like are released from the chamber (fourthstep).

Note that the introduction of a reactant at the third step and theintroduction of an inert gas at the fourth step may be repeatedlyperformed. That is, after the first step and the second step areperformed, the third step, the fourth step, the third step, and thefourth step may be performed, for example.

For example, it is possible to introduce O₃ as an oxidizer at the thirdstep, to perform N₂ purging at the fourth step, and to repeat thesesteps.

In the case where the third and fourth steps are repeated, the samereactant is not necessarily used for the repeated introduction. Forexample, H₂O may be used as an oxidizer at the third step (for the firsttime), and O₃ may be used as an oxidizer at the third steps (at thesecond and subsequent times).

As described above, the introduction of an oxidizer and the introductionof an inert gas (or vacuum evacuation) in the chamber are repeatedmultiple times in a short time, whereby excess hydrogen atoms and thelike can be more certainly removed from the precursor adsorbed onto thesubstrate surface and eliminated from the chamber. In the case where twokinds of oxidizers are introduced, more excess hydrogen atoms and thelike can be removed from the precursor adsorbed onto the substratesurface. In this manner, hydrogen atoms are prevented from entering theinsulator 103 and the like during the deposition, so that the amounts ofwater, hydrogen, and the like in the insulator 103 and the like can besmall.

By the above-described method, the insulator 103 releases watermolecules, the number of which is greater than or equal to 1.0×10¹³molecules/cm² and less than or equal to 1.0×10¹⁶ molecules/cm² andpreferably greater than or equal to 1.0×10¹³ molecules/cm² and less thanor equal to 3.0×10¹⁵ molecules/cm² in TDS analysis in the range of asurface temperature from 100° C. to 700° C. or from 100° C. to 500° C.

A first single layer can be formed on the substrate surface in the abovemanner. By performing the first to fourth steps again, a second singlelayer can be stacked over the first single layer. With the introductionof gases controlled, the first to fourth steps are repeated plural timesuntil a film having a desired thickness is obtained, whereby a thin filmwith excellent step coverage can be formed. The thickness of the thinfilm can be adjusted by the number of repetition times; therefore, anALD method makes it possible to adjust a thickness accurately and thusis suitable for fabricating a minute transistor.

In an ALD method, a film is formed through reaction of the precursorusing thermal energy. An ALD method in which the reactant becomes aradical state with the use of plasma in the above-described reaction ofthe reactant is sometimes called a plasma ALD method. An ALD method inwhich reaction between the precursor and the reactant is performed usingthermal energy is sometimes called a thermal ALD method.

By an ALD method, an extremely thin film can be formed to have a uniformthickness. In addition, the coverage of an uneven surface with the filmis high.

When the plasma ALD method is employed, the film can be formed at alower temperature than when the thermal ALD method is employed. With theplasma ALD method, for example, the film can be formed withoutdecreasing the deposition rate even at 100° C. or lower. Furthermore, inthe plasma ALD method, any of a variety of reactants, including anitrogen gas, can be used without being limited to an oxidizer;therefore, it is possible to form various kinds of films of not only anoxide but also a nitride, a fluoride, a metal, and the like.

In the case where the plasma ALD method is employed, as in aninductively coupled plasma (ICP) method or the like, plasma can begenerated apart from a substrate. When plasma is generated in thismanner, plasma damage can be minimized.

Here, a structure of a deposition apparatus 1000 is described withreference to FIGS. 16A and 16B as an example of an apparatus with whicha film can be formed by an ALD method. FIG. 16A is a schematic diagramof a multi-chamber deposition apparatus 1000, and FIG. 16B is across-sectional view of an ALD apparatus that can be used for thedeposition apparatus 1000.

<<Example of Structure of Deposition Apparatus>>

The deposition apparatus 1000 includes a carrying-in chamber 1002, acarrying-out chamber 1004, a transfer chamber 1006, a deposition chamber1008, a deposition chamber 1009, a deposition chamber 1010, and atransfer arm 1014. Here, the carrying-in chamber 1002, the carrying-outchamber 1004, and the deposition chambers 1008 to 1010 are connected tothe transfer chamber 1006. Thus, successive film formation can beperformed in the deposition chambers 1008 to 1010 without exposure tothe air, whereby entry of impurities into a film can be prevented.

Note that in order to prevent attachment of moisture, the carrying-inchamber 1002, the carrying-out chamber 1004, the transfer chamber 1006,and the deposition chambers 1008 to 1010 are preferably filled with aninert gas (such as a nitrogen gas) whose dew point is controlled, morepreferably maintain reduced pressure.

An ALD apparatus can be used for the deposition chambers 1008 to 1010. Adeposition apparatus other than an ALD apparatus may be used for any ofthe deposition chambers 1008 to 1010. Examples of the depositionapparatus used for the deposition chambers 1008 to 1010 include asputtering apparatus, a PECVD apparatus, a TCVD apparatus, and an MOCVDapparatus.

For example, when an ALD apparatus and a PECVD apparatus are provided inthe deposition chambers 1008 to 1010, the insulator 105 made of siliconoxide and included in the transistor 10 in FIGS. 1B and 1C can be formedby a PECVD method, the insulator 103 made of hafnium oxide can be formedby an ALD method, and the insulator 104 made of silicon oxide containinghalogen can be formed by a PECVD method. Because the series of filmformation is successively performed without exposure to the air, filmscan be formed without entry of impurities into the films.

Although the deposition apparatus 1000 includes the carrying-in chamber1002, the carrying-out chamber 1004, and the deposition chambers 1008 to1010, the present invention is not limited to this structure. Thedeposition apparatus 1000 may have four or more deposition chambers, ormay additionally include a treatment chamber for heat treatment orplasma treatment. The deposition apparatus 1000 may be of a single-wafertype or may be of a batch type, in which case film formation isperformed on a plurality of substrates at a time.

<<ALD Apparatus>>

Next, a structure of an ALD apparatus that can be used for thedeposition apparatus 1000 is described. The ALD apparatus includes adeposition chamber (chamber 1020), source material supply portions 1021a and 1021 b, high-speed valves 1022 a and 1022 b which are flow ratecontrollers, source material introduction ports 1023 a and 1023 b, asource material exhaust port 1024, and an evacuation unit 1025. Thesource material introduction ports 1023 a and 1023 b provided in thechamber 1020 are connected to the source material supply portions 1021 aand 1021 b, respectively, through supply tubes and valves. The sourcematerial exhaust port 1024 is connected to the evacuation unit 1025through an exhaust tube, a valve, and a pressure controller.

A plasma generation apparatus 1028 is connected to the chamber 1020 asillustrated in FIG. 16B, whereby film formation can be performed by aplasma ALD method instead of a thermal ALD method. By a plasma ALDmethod, a film can be formed without decreasing the deposition rate evenat low temperatures; thus, a plasma ALD method is preferably used for asingle-wafer type deposition apparatus with low deposition efficiency.

A substrate holder 1026 with a heater is provided in the chamber, and asubstrate 1030 over which a film is to be formed is provided over thesubstrate holder 1026.

In the source material supply portions 1021 a and 1021 b, a source gasis formed from a solid source material or a liquid source material byusing a vaporizer, a heating unit, or the like. Alternatively, thesource material supply portions 1021 a and 1021 b may supply a sourcegas.

Although two source material supply portions 1021 a and 1021 b areprovided as an example, the number of source material supply portions isnot limited thereto, and three or more source material supply portionsmay be provided. The high-speed valves 1022 a and 1022 b can beaccurately controlled by time, and a source gas and an inert gas aresupplied by the high-speed valves 1022 a and 1022 b. The high-speedvalves 1022 a and 1022 b are flow rate controllers for a source gas, andcan also be referred to as flow rate controllers for an inert gas.

In the deposition apparatus illustrated in FIG. 16B, a thin film isformed over a surface of the substrate 1030 in the following manner: thesubstrate 1030 is transferred to be put on the substrate holder 1026,the chamber 1020 is sealed, the substrate 1030 is heated to a desiredtemperature (e.g., higher than or equal to 80° C., higher than or equalto 100° C., or higher than or equal to 150° C.) by heating the substrateholder 1026 with a heater; and supply of a source gas, evacuation withthe evacuation unit 1025, supply of an inert gas, and evacuation withthe evacuation unit 1025 are repeated.

In the deposition apparatus illustrated in FIG. 16B, an insulating layerformed using an oxide (including a composite oxide) containing one ormore elements selected from hafnium, aluminum, tantalum, zirconium, andthe like can be formed by selecting a source material (e.g., a volatileorganometallic compound) used for the source material supply portions1021 a and 1021 b appropriately. Specifically, it is possible to use aninsulating layer formed using hafnium oxide, an insulating layer formedusing aluminum oxide, an insulating layer formed using hafnium silicate,or an insulating layer formed using aluminum silicate. Alternatively, athin film, e.g., a metal layer such as a tungsten layer or a titaniumlayer, or a nitride layer such as a titanium nitride layer can be formedby selecting a source material (e.g., a volatile organometalliccompound) used for the source material supply portions 1021 a and 1021 bappropriately.

For example, in the case where a hafnium oxide layer is formed by an ALDapparatus, two kinds of gases, i.e., ozone (O₃) as an oxidizer and asource gas which is obtained by vaporizing liquid containing a solventand a hafnium precursor compound (hafnium alkoxide or hafnium amide suchas tetrakis(dimethylamido)hafnium (TDMAH)) are used. In this case, thefirst source gas supplied from the source material supply portion 1021 ais TDMAH, and the second source gas supplied from the source materialsupply portion 1021 b is ozone. Note that the chemical formula oftetrakis(dimethylamido)hafnium is Hf[N(CH₃)₂]₄. Examples of anothermaterial liquid include tetrakis(ethylmethylamido)hafnium.

For example, in the case where an aluminum oxide layer is formed by anALD apparatus, two kinds of gases, i.e., H₂O as an oxidizer and a sourcegas which is obtained by vaporizing a liquid containing a solvent and analuminum precursor compound (e.g., trimethylaluminum (TMA)) are used. Inthis case, the first source gas supplied from the source material supplyportion 1021 a is TMA, and the second source gas supplied from thesource material supply portion 1021 b is H₂O. Note that the chemicalformula of trimethylaluminum is Al(CH₃)₃. Examples of another materialliquid include tris(dimethylamido)aluminum, triisobutylaluminum, andaluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate).

In the case where a tungsten layer is formed using an ALD apparatus, aWF₆ gas and a B₂H₆ gas are sequentially introduced a plurality of timesto form an initial tungsten layer, and then a WF₆ gas and an H₂ gas aresequentially introduced a plurality of times to form a tungsten layer.Note that an SiH₄ gas may be used instead of a B₂H₆ gas. These gases maybe controlled by mass flow controllers.

Then, the insulator 104 is formed (see FIGS. 13C and 13D). Any of theabove-described insulators can be used for the insulator 104. Theinsulator 104 can be formed by a sputtering method, a CVD method, an MBEmethod, a PLD method, an ALD method, or the like.

A CVD method, in particular, a PECVD method is preferably used for theformation of the insulator 104.

In the case where the insulator 104 is formed by a PECVD method, asubstance without containing hydrogen or a substance containing a smallamount of hydrogen is preferably used as a source gas; for example, ahalide is preferably used. For example, in the case where silicon oxideor silicon oxynitride is deposited as the insulator 104, silicon halideis preferably used as a source gas. As the silicon halide, for example,silicon tetrafluoride (SiF₄), silicon tetrachloride (SiCl₄), silicontrichloride (SiHCl₃), dichlorosilane (SiH₂Cl₂), or silicon tetrabromide(SiBr₄) can be used.

In the case where the insulator 104 is formed by a PECVD method, anoxidation gas (e.g., N₂O) is introduced. Since the above-describedsilicon halides are less reactive than SiH₄, the oxidation gas readilyinteracts with the insulator 103. Accordingly, there is a possibilitythat water and hydrogen in the insulator 103 can be released by theoxidation gas, and the amounts of water and hydrogen in the insulator103 can be reduced.

When a silicon halide is used as the source gas for the formation of theinsulator 104, a silicon hydride may be used in addition to the siliconhalide. In that case, the amounts of hydrogen and water in the insulator104 can be reduced as compared with the case where only a siliconhydride is used as the source gas, and the deposition rate can beimproved as compared with the case where only a silicon halide is usedas the source gas. For example, SiF₄ and SiH₄ may be used as the sourcegas for the formation of the insulator 104. For example, the flow rateof SiH₄ is set to greater than 1 sccm and less than 10 sccm, preferably,greater than or equal to 2 sccm and less than or equal to 4 sccm, inwhich case the amounts of water and hydrogen in the insulator 104 andthe deposition rate can be relatively favorable values. Note that theflow ratio of SiF₄ to SiH₄ can be determined as appropriate in view ofthe amounts of water and hydrogen in the insulator 104 and thedeposition rate.

In order to reduce water and hydrogen contained in the insulator 104,the insulator 104 may be formed while the substrate is being heated. Forexample, in the case where a semiconductor element layer is providedunder the transistor 10 and the heat treatment is performed in arelatively low temperature range (e.g., higher than or equal to 350° C.and lower than or equal to 445° C.), water, hydrogen, and the like inthe insulator 104 can be sufficiently removed by the method for formingthe insulator 104 to be described later.

Furthermore, introduction of SiH₄ into the chamber before the formationof the insulator 104 over the substrate makes it relatively easy to forma silicon oxide film containing fluorine over a hafnium oxide filmthough the silicon oxide film containing fluorine is generally difficultto form over the hafnium oxide film.

By the above-described method, the insulator 104 releases watermolecules, the number of which is greater than or equal to 1.0×10¹³molecules/cm² and less than or equal to 1.4×10¹⁶ molecules/cm²,preferably greater than or equal to 1.0×10¹³ molecules/cm² and less thanor equal to 4.0×10¹⁵ molecules/cm², more preferably greater than orequal to 1.0×10¹³ molecules/cm² and less than or equal to 2.0×10¹⁵molecules/cm² in TDS analysis in the range of a surface temperature from100° C. to 700° C. or from 100° C. to 500° C. The insulator 104 releaseshydrogen molecules, the number of which is greater than or equal to1.0×10¹³ molecules/cm² and less than or equal to 1.2×10¹⁵ molecules/cm²,preferably greater than or equal to 1.0×10¹³ molecules/cm² and less thanor equal to 9.0×10¹⁴ molecules/cm² in TDS analysis in the range of asurface temperature from 100° C. to 700° C. or from 100° C. to 500° C.

The top surface or the bottom surface of the semiconductor 106 b to beformed later preferably has high planarity. Thus, to improve theplanarity, the top surface of the insulator 104 may be subjected toplanarization treatment such as CMP treatment.

Next, heat treatment is preferably performed. The heat treatment canfurther reduce water and hydrogen in the insulator 105, the insulator103, and the insulator 104. In addition, the insulator 104 can containexcess oxygen in some cases. The heat treatment may be performed at atemperature higher than or equal to 250° C. and lower than or equal to650° C., preferably higher than or equal to 450° C. and lower than orequal to 600° C., further preferably higher than or equal to 520° C. andlower than or equal to 570° C. The heat treatment is performed in aninert gas atmosphere or an atmosphere containing an oxidizing gas at 10ppm or more, 1% or more, or 10% or more. The heat treatment may beperformed under a reduced pressure. Alternatively, the heat treatmentmay be performed in such a manner that heat treatment is performed in aninert gas atmosphere, and then another heat treatment is performed in anatmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or10% or more in order to compensate desorbed oxygen. The heat treatmentcan increase the crystallinity of the insulator 126 a and thesemiconductor 126 b and can remove impurities, such as hydrogen andwater, for example. For the heat treatment, lamp heating can beperformed with use of an RTA apparatus. Heat treatment with an RTAapparatus is effective for an improvement in productivity because itneeds short time as compared with the case of using a furnace.

Note that in the case where a semiconductor element layer is providedbelow the transistor 10, the heat treatment can be performed in arelatively low temperature range (e.g., higher than or equal to 350° C.and lower than or equal to 445° C.). For example, the temperature ispreferably set lower than or equal to the highest heating temperatureamong the substrate heating temperatures for forming the insulator 105,the insulator 103, and the insulator 104.

Next, an insulator 126 a is formed. Any of the above-describedinsulators and semiconductors that can be used for the insulator 106 acan be used for the insulator 126 a. The insulator 126 a can be formedby a sputtering method, a CVD method, an MBE method, a PLD method, anALD method, or the like.

Next, a semiconductor 126 b is formed. Any of the above-describedsemiconductors that can be used for the semiconductor 106 b can be usedfor the semiconductor 126 b. The semiconductor 126 b can be formed by asputtering method, a CVD method, an MBE method, a PLD method, an ALDmethod, or the like. Note that successive film formation of theinsulator 126 a and the semiconductor 126 b without exposure to the aircan reduce entry of impurities into the films and their interface.

Next, heat treatment is preferably performed. The heat treatment canreduce the hydrogen concentration of the insulator 126 a and thesemiconductor 126 b in some cases. The heat treatment can reduce oxygenvacancies in the insulator 126 a and the semiconductor 126 b in somecases. The heat treatment may be performed at a temperature higher thanor equal to 250° C. and lower than or equal to 650° C., preferablyhigher than or equal to 450° C. and lower than or equal to 600° C.,further preferably higher than or equal to 520° C. and lower than orequal to 570° C. The heat treatment is performed in an inert gasatmosphere or an atmosphere containing an oxidizing gas at 10 ppm ormore, 1% or more, or 10% or more. The heat treatment may be performedunder a reduced pressure. Alternatively, the heat treatment may beperformed in such a manner that heat treatment is performed in an inertgas atmosphere, and then another heat treatment is performed in anatmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or10% or more in order to compensate desorbed oxygen. The heat treatmentcan increase the crystallinity of the insulator to be the insulator 106a, the semiconductor to be the semiconductor 106 b, and the insulator tobe the insulator 106 c and can remove impurities, such as hydrogen andwater, for example. For the heat treatment, lamp heating can beperformed with use of an RTA apparatus. Heat treatment with an RTAapparatus is effective for an improvement in productivity because itneeds short time as compared with the case of using a furnace. By heattreatment, the peak intensity is increased and a full width at halfmaximum is decreased when a CAAC-OS is used for the insulator 126 a andthe semiconductor 126 b. In other words, the crystallinity of a CAAC-OSis increased by heat treatment.

Note that in the case where a semiconductor element layer is providedbelow the transistor 10, the heat treatment can be performed in arelatively low temperature range (e.g., higher than or equal to 350° C.and lower than or equal to 445° C.). For example, the temperature ispreferably set lower than or equal to the highest heating temperatureamong the substrate heating temperatures for forming the insulator 105,the insulator 103, and the insulator 104 and the temperature of the heattreatment after the formation of the insulator 104. Since water,hydrogen, and the like in the insulator 104 can be sufficiently smallwhen the above-described method for forming the insulator 104 isemployed, water and hydrogen supplied to the insulator 126 a and thesemiconductor 126 b can be sufficiently reduced.

By the heat treatment, oxygen can be supplied from the insulator 104 tothe insulator 126 a and the semiconductor 126 b. The heat treatmentperformed on the insulator 104 makes it very easy to supply oxygen tothe insulator 126 a and the semiconductor 126 b.

Here, the insulator 103 serves as a barrier film that blocks oxygen. Theinsulator 103 provided under the insulator 104 can prevent oxygendiffused in the insulator 104 from being diffused into layers under theinsulator 104.

Oxygen is supplied to the insulator 126 a and the semiconductor 126 b toreduce oxygen vacancies, whereby highly purified intrinsic orsubstantially highly purified intrinsic oxide semiconductor with a lowdensity of defect states can be achieved.

High-density plasma treatment or the like may be performed. High-densityplasma may be generated using microwaves. For the high-density plasmatreatment, for example, an oxidation gas such as oxygen or nitrous oxidemay be used. Alternatively, a mixed gas of an oxidation gas and a raregas such as He, Ar, Kr, or Xe may be used. In the high-density plasmatreatment, a bias may be applied to the substrate. Thus, oxygen ions andthe like in the plasma can be extracted to the substrate side. Thehigh-density plasma treatment may be performed while the substrate isbeing heated. For example, in the case where the high-density plasmatreatment is performed instead of the heat treatment, the similar effectcan be obtained at a temperature lower than the heat treatmenttemperature. The high-density plasma treatment may be performed beforethe formation of the insulator 126 a, after the formation of theinsulator 112, or after the formation of the insulator 116.

Next, a conductor 128 is formed (see FIGS. 13E and 13F). Any of theabove-described conductors that can be used for the conductors 108 a and108 b can be used for the conductor 128. The conductor 128 can be formedby a sputtering method, a CVD method, an MBE method, a PLD method, anALD method, or the like.

Next, a resist or the like is formed over the conductor 128 andprocessing is performed using the resist or the like, whereby theconductors 108 a and 108 b are formed.

Next, a resist or the like is formed over the semiconductor 126 b andprocessing is performed using the resist or the like and the conductors108 a and 108 b, whereby the insulator 106 a and the semiconductor 106 bare formed (see FIGS. 13G and 13H).

Here, regions of the semiconductor 106 b that are in contact with theconductor 108 a and the conductor 108 b include the low-resistanceregion 109 a and the low-resistance region 109 b in some cases. Thesemiconductor 106 b might have a smaller thickness in a region betweenthe conductor 108 a and the conductor 108 b than in regions overlappingwith the conductor 108 a and the conductor 108 b. This is because partof the top surface of the semiconductor 106 b is sometimes removed atthe time of the formation of the conductor 108 a and the conductor 108b.

Next, heat treatment is preferably performed. The heat treatment canfurther reduce water and hydrogen in the insulator 104, the insulator103, the insulator 105, the insulator 106 a, and the semiconductor 106b. The heat treatment is performed at a temperature higher than or equalto 250° C. and lower than or equal to 650° C., preferably higher than orequal to 450° C. and lower than or equal to 600° C., further preferablyhigher than or equal to 520° C. and lower than or equal to 570° C. Theheat treatment may be performed in an inert gas atmosphere. The heattreatment may be performed in an atmosphere containing an oxidizing gas.The heat treatment may be performed under a reduced pressure.Alternatively, the heat treatment may be performed in such a manner thatheat treatment is performed in an inert gas atmosphere, and then anotherheat treatment is performed in an atmosphere containing an oxidizing gasat 10 ppm or more, 1% or more, or 10% or more in order to compensatedesorbed oxygen. For the heat treatment, lamp heating can be performedwith use of an RTA apparatus. Heat treatment with an RTA apparatus iseffective for an improvement in productivity because it needs short timeas compared with the case of using a furnace.

Note that in the case where a semiconductor element layer is providedbelow the transistor 10, the heat treatment is preferably performed in arelatively low temperature range (e.g., higher than or equal to 350° C.and lower than or equal to 445° C.) in order not to degrade thesemiconductor element layer in a lower layer.

In the case where the insulator 104 contains much water and hydrogen atthe time of being formed, such heat treatment in a temperature rangethat does not degrade the semiconductor element layer in the lower layercannot remove the water, hydrogen, and the like sufficiently from theinsulator 104 in some cases. Moreover, if heat treatment in such atemperature range is performed after formation of the insulator 106 c,water, hydrogen, and the like might be supplied from the insulator 104to the semiconductor 106 b and the like, forming defect states.

In contrast, when the heat treatment is performed at the stage where theinsulator 106 a and the semiconductor 106 b are formed and a surface ofthe insulator 104 is exposed, as described above, it is possible toinhibit supply of water and hydrogen to the insulator 106 a and thesemiconductor 106 b and to further reduce water and hydrogen in theinsulator 104, the insulator 103, and the insulator 105. When water andhydrogen in the insulator 104, the insulator 103, and the insulator 105are further reduced, heating at a relatively low temperature (e.g.,higher than or equal to 350° C. and lower than or equal to 445° C.) cansufficiently remove water, hydrogen, and the like so that defect statescan be prevented from being formed in the semiconductor 106 b and thelike. In this manner, it is possible to provide a highly reliabletransistor.

In the case where an etching gas containing impurities such as hydrogenand carbon are used for the formation of the insulator 106 a and thesemiconductor 106 b, the impurities such as hydrogen and carbonsometimes enter the insulator 106 a, the semiconductor 106 b, and thelike. The impurities such as hydrogen and carbon that enter theinsulator 106 a and the semiconductor 106 b at the time of etching canbe released by heat treatment performed after the formation of theinsulator 106 a and the semiconductor 106 b.

The high-density plasma treatment may be performed instead of the heattreatment. Alternatively, the high-density plasma treatment may beperformed after the heat treatment. In this manner, impurities such ashydrogen and carbon in the semiconductor 106 b and the like can bereleased and oxygen vacancies can be filled with oxygen.

Note that after formation of the conductor 128, the insulator 126 a, thesemiconductor 126 b, and the conductor 128 may be collectively processedto form the insulator 106 a, the semiconductor 106 b, and a conductorhaving a shape overlapping with the semiconductor 106 b, and theconductor having the shape overlapping with the semiconductor 106 b maybe further processed to form the conductor 108 a and the conductor 108b.

Then, the insulator 126 c is formed. Any of the above-describedinsulators or semiconductors that can be used for the insulator 106 ccan be used for the insulator 126 c, for example. The insulator 126 ccan be formed by a sputtering method, a CVD method, an MBE method, a PLDmethod, an ALD method, or the like. Before the formation of theinsulator 126 c, surfaces of the semiconductor 106 b, the conductor 108a, and the conductor 108 b may be etched. For example, plasma containinga rare gas can be used for the etching. After that, the insulator 126 cis successively formed without being exposed to the air, wherebyimpurities can be prevented from entering interfaces between theinsulator 106 c and the semiconductor 106 b, the conductor 108 a, andthe conductor 108 b. In some cases, impurities at an interface betweenfilms are diffused more easily than impurities in a film. For thisreason, a reduction in impurity at the interfaces leads to stableelectrical characteristics of a transistor.

Then, the insulator 132 is formed. Any of the above-described insulatorsthat can be used for the insulator 112 can be used for the insulator132. The insulator 132 can be formed by a sputtering method, a CVDmethod, an MBE method, a PLD method, an ALD method, or the like. Notethat successive film formation of the insulator 126 c and the insulator132 without exposure to the air can reduce entry of impurities into thefilms and their interface.

Next, the conductor 134 is formed (see FIGS. 14A and 14B). Any of theabove-described conductors that can be used for the conductor 114 can beused for the conductor 134. The conductor 134 can be formed by asputtering method, a CVD method, an MBE method, a PLD method, an ALDmethod, or the like. Note that successive film formation of theinsulator 132 and the conductor 134 without exposure to the air canreduce entry of impurities into the films and their interface.

Next, a resist or the like is formed over the conductor 134 andprocessing is performed using the resist, whereby the conductor 114 isformed.

Then, a resist or the like is formed over the conductor 114 and theinsulator 132 and processing is performed using the resist, whereby theinsulator 106 c and the insulator 112 are formed (see FIGS. 14C and14D). Note that at this time, the insulator 106 c and the insulator 112may be formed to expose regions where the conductor 120 a and theconductor 120 b that are formed later are in contact with the conductor108 a and the conductor 108 b.

Then, the insulator 116 is formed (see FIGS. 14E and 14F). Any of theabove-described insulators can be used for the insulator 116. Theinsulator 116 can be formed by a sputtering method, a CVD method, an MBEmethod, a PLD method, an ALD method, or the like.

Here, as the insulator 116, an oxide insulating film of aluminum oxideor the like having a blocking effect against oxygen, hydrogen, water, orthe like is preferably provided.

The insulator 116 is preferably formed by utilizing plasma, furtherpreferably a sputtering method, still further preferably a sputteringmethod in an atmosphere containing oxygen.

As the sputtering method, a direct current (DC) sputtering method inwhich a direct-current power source is used as a sputtering powersource, a DC sputtering method in which a pulsed bias is applied (i.e.,a pulsed DC sputtering method), or a radio frequency (RF) sputteringmethod in which a high frequency power source is used as a sputteringpower source may be used. Alternatively, a magnetron sputtering methodusing a magnet mechanism inside a chamber, a bias sputtering method inwhich voltage is also applied to a substrate during deposition, areactive sputtering method performed in a reactive gas atmosphere, orthe like may be used. Further alternatively, the above-described PESP orVDSP method may be used. The oxygen gas flow rate or deposition powerfor sputtering can be set as appropriate in accordance with the amountof oxygen to be added.

When the insulator 116 is formed by a sputtering method, oxygen is addedto the vicinity of a surface of the insulator 104 or a surface of theinsulator 112 (after the formation of the insulator 116, an interfacebetween the insulator 116 and the insulator 104 or the insulator 112) atthe same time as the formation. Although the oxygen is added to theinsulator 104 or the insulator 104 as an oxygen radical, for example,the state of the oxygen at the time of being added is not limitedthereto. The oxygen may be added to the insulator 104 or the insulator112 as an oxygen atom, an oxygen ion, or the like. Note that by additionof oxygen, oxygen in excess of the stoichiometric composition iscontained in the insulator 104 or the insulator 112 in some cases, andthe oxygen in such a case can be called excess oxygen.

Next, heat treatment is preferably performed (see FIGS. 15A and 15B). Bythe heat treatment, oxygen added to the insulator 104 or the insulator112 can be diffused to be supplied to the insulator 106 a, thesemiconductor 106 b, and the insulator 106 c. The heat treatment isperformed at a temperature higher than or equal to 250° C. and lowerthan or equal to 650° C., preferably higher than or equal to 350° C. andlower than or equal to 450° C. The heat treatment is performed in aninert gas atmosphere or an atmosphere containing an oxidizing gas at 10ppm or more, 1% or more, or 10% or more. The heat treatment may beperformed under a reduced pressure. For the heat treatment, lamp heatingcan be performed with use of an RTA apparatus.

This heat treatment is preferably performed at a temperature lower thanthat of the heat treatment performed after formation of thesemiconductor 126 b. A temperature difference between the heat treatmentand the heat treatment performed after formation of the semiconductor126 b is to be 20° C. or more and 150° C. or less, preferably 40° C. ormore and 100° C. or less. Accordingly, superfluous release of excessoxygen (oxygen) from the insulator 104 and the like can be inhibited.Note that in the case where heating at the time of formation of thelayers (e.g., heating at the time of formation of the insulator 118)doubles as the heat treatment after formation of the insulator 118, theheat treatment after formation of the insulator 118 is not necessarilyperformed.

Oxygen (hereinafter referred to as an oxygen 186) added to the insulator104 and the insulator 112 by the deposition of the insulator 116 isdiffused in the insulator 104 or the insulator 112 by the heat treatment(see FIGS. 15A and 15B). The insulator 116 is less permeable to oxygenthan the insulator 104 or the insulator 112 and functions as a barrierfilm that blocks oxygen. Since the insulator 116 is provided over theinsulator 104 or the insulator 112, the oxygen 186 diffused in theinsulator 104 or the insulator 112 is prevented from being diffused inlayers over the insulator 104 or the insulator 112, so that the oxygen186 is diffused mainly laterally or downward in the insulator 104 or theinsulator 112.

The oxygen 186 that is diffused in the insulator 104 or the insulator112 is supplied to the insulator 106 a, the insulator 106 c, and thesemiconductor 106 b. Here, the insulator 103 serves as a barrier filmthat blocks. The insulator 103 having a function of blocking oxygenprovided under the insulator 104 can prevent oxygen diffused in theinsulator 104 from being diffused into layers under the insulator 104.

Thus, the oxygen 186 can be effectively supplied to the insulator 106 a,the insulator 106 c, and the semiconductor 106 b, especially to achannel formation region in the semiconductor 106 b. Oxygen is suppliedto the insulator 106 a, the insulator 106 c, and the semiconductor 106 bto reduce oxygen vacancies in this manner, whereby a highly purifiedintrinsic or substantially highly purified intrinsic oxide semiconductorwith a low density of defect states can be achieved.

Note that heat treatment after the formation of the insulator 116 may beperformed at any time after the insulator 116 is formed. For example,the heat treatment may be performed after the insulator 118 is formed orafter the conductors 120 a and 120 b are formed.

Next, the insulator 118 is formed. Any of the above-described insulatorscan be used for the insulator 118. The insulator 118 can be formed by asputtering method, a CVD method, an MBE method, a PLD method, an ALDmethod, or the like.

Next, a resist or the like is formed over the insulator 118, andopenings are formed in the insulator 118, the insulator 116, theinsulator 112, and the insulator 106 c. Then, a conductor to be theconductor 120 a and the conductor 120 b is formed. Any of theabove-described conductors can be used for the conductor to be theconductor 120 a and the conductor 120 b. The conductor can be formed bya sputtering method, a CVD method, an MBE method, a PLD method, an ALDmethod, or the like.

Next, a resist or the like is formed over the conductor and processingis performed using the resist or the like, whereby the conductors 120 aand 120 b are formed (see FIGS. 15C and 15D).

Through the above process, the transistor of one embodiment of thepresent invention can be fabricated.

A method for fabricating the transistor 29 is described below withreference to FIGS. 17A to 17H, FIGS. 18A to 18F, and FIGS. 19A to 19F.Note that for the method for fabricating the transistor 29, any of theabove-mentioned methods for fabricating a transistor can be referred to,as appropriate.

First, the substrate 100 is prepared. Any of the above-mentionedsubstrates can be used for the substrate 100.

Next, the insulator 101 is formed. Any of the above-mentioned insulatorscan be used for the insulator 101.

Then, an insulator to be the insulator 107 is formed. Any of theabove-described insulators can be used for the insulator. The insulatorcan be formed by a sputtering method, a CVD method, an MBE method, a PLDmethod, an ALD method, or the like.

Next, a resist or the like is formed over the insulator and processingis performed using the resist or the like, whereby the insulator 107having an opening is formed.

Next, a conductor to be the conductor 102 is formed. Any of theabove-described conductors can be used for the conductor to be theconductor 102. The conductor can be formed by a sputtering method, a CVDmethod, an MBE method, a PLD method, an ALD method, or the like.

Next, the conductor is polished until the insulator 107 is exposed,whereby the conductor 102 is formed (see FIGS. 17A and 17B). Forexample, CMP treatment may be performed as the polishing.

Then, the insulator 105 is formed. Any of the above-described insulatorscan be used for the insulator 105. The insulator 105 can be formed by asputtering method, a CVD method, an MBE method, a PLD method, an ALDmethod, or the like. In order to reduce water and hydrogen contained inthe insulator 105, the insulator 105 may be formed while the substrateis being heated. For example, in the case where a semiconductor elementlayer is provided below the transistor 29, the heat treatment may beperformed in a relatively low temperature range (e.g., higher than orequal to 350° C. and lower than or equal to 445° C.).

Alternatively, the insulator 105 may be formed by a PECVD method in amanner similar to that of the insulator 104 described above in order toreduce water and hydrogen contained in the insulator 105.

Then, the insulator 103 is formed. Any of the above-described insulatorscan be used for the insulator 103. The insulator 103 can be formed by asputtering method, a CVD method, an MBE method, a PLD method, an ALDmethod, or the like. In order to reduce water and hydrogen contained inthe insulator 103, the insulator 103 may be formed while the substrateis being heated. For example, in the case where a semiconductor elementlayer is provided under the transistor 10, the heat treatment may beperformed in a relatively low temperature range (e.g., higher than orequal to 350° C. and lower than or equal to 445° C.).

Then, the insulator 104 is formed (see FIGS. 17C and 17D). Any of theabove-described insulators can be used for the insulator 104. Theinsulator 104 can be formed by a sputtering method, a CVD method, an MBEmethod, a PLD method, an ALD method, or the like.

The top surface or the bottom surface of the semiconductor 106 b to beformed later preferably has high planarity. Thus, to improve theplanarity, the top surface of the insulator 104 may be subjected toplanarization treatment such as CMP treatment.

Next, heat treatment is preferably performed.

Next, an insulator to be the insulator 106 a is formed. Any of theabove-described insulators and semiconductors that can be used for theinsulator 106 a can be used for the insulator. The insulator can beformed by a sputtering method, a CVD method, an MBE method, a PLDmethod, an ALD method, or the like.

Next, a semiconductor to be the semiconductor 106 b is formed. Any ofthe above-described semiconductors that can be used for thesemiconductor 106 b can be used for the semiconductor. The semiconductorcan be formed by a sputtering method, a CVD method, an MBE method, a PLDmethod, an ALD method, or the like. Note that successive film formationof the insulator and the semiconductor without exposure to the air canreduce entry of impurities into the films and their interface.

Next, heat treatment is preferably performed. The heat treatment canfurther reduce water and hydrogen in the insulator 105, the insulator103, and the insulator 104. In addition, the insulator 104 can containexcess oxygen in some cases. The heat treatment may be performed at atemperature higher than or equal to 250° C. and lower than or equal to650° C., preferably higher than or equal to 450° C. and lower than orequal to 600° C., further preferably higher than or equal to 520° C. andlower than or equal to 570° C. The heat treatment is performed in aninert gas atmosphere or an atmosphere containing an oxidizing gas at 10ppm or more, 1% or more, or 10% or more. The heat treatment may beperformed under a reduced pressure. Alternatively, the heat treatmentmay be performed in such a manner that heat treatment is performed in aninert gas atmosphere, and then another heat treatment is performed in anatmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or10% or more in order to compensate desorbed oxygen. The heat treatmentcan increase the crystallinity of the insulator to be the insulator 106a and the semiconductor to be the semiconductor 106 b and can removeimpurities, such as hydrogen and water, for example. For the heattreatment, lamp heating can be performed with use of an RTA apparatus.Heat treatment with an RTA apparatus is effective for an improvement inproductivity because it needs short time as compared with the case ofusing a furnace.

Note that in the case where a semiconductor element layer is providedbelow the transistor 10, the heat treatment can be performed in arelatively low temperature range (e.g., higher than or equal to 350° C.and lower than or equal to 445° C.). For example, the temperature ispreferably set lower than or equal to the highest heating temperatureamong the substrate heating temperatures for forming the insulator 105,the insulator 103, and the insulator 104.

Here, a silicon halide such as SiF₄ is used for the formation of theinsulator 104, halogen such as fluorine is contained in the insulator104. Oxygen in the insulator 104 is replaced with fluorine during theheat treatment, so that the oxygen is released (SiO+F→SiF+O) and issupplied to an insulator to be the insulator 106 a and a semiconductorto be the semiconductor 106 b. The mechanism is described below.

<Silicon Oxide Including Fluorine>

As an example of the insulator including excess oxygen, a silicon oxideincluding fluorine is described below with reference to FIGS. 74A and74B.

A silicon oxide (Sift) includes two oxygen atoms with respect to onesilicon atom. As illustrated in FIG. 74A, one silicon atom is bonded tofour oxygen atoms, and one oxygen atom is bonded to two silicon atoms.

When two fluorine atoms enter the silicon oxide, bonds of one oxygenatom to two silicon atoms are cut ( . . . Si—O—Si . . . +2F→ . . .Si—O—Si . . . +2F). Then, the fluorine atoms are bonded to the siliconatoms whose bonds to the oxygen atom have been cut ( . . . Si—O—Si . . .+2F→ . . . Si—F F—Si . . . +O). At this time, the oxygen atom whosebonds have been cut becomes excess oxygen (see FIG. 74B).

The excess oxygen included in silicon oxide can reduce oxygen vacanciesin the oxide semiconductor. Oxygen vacancies in the oxide semiconductorserve as hole traps or the like. Accordingly, excess oxygen included insilicon oxide can lead to stable electrical characteristics of thetransistor.

As described above, when fluorine is included in silicon oxide,generation of excess oxygen occurs. Note that in the case where excessoxygen is consumed to reduce oxygen vacancies in the oxidesemiconductor, the amount of oxygen in the silicon oxide becomes smallerthan that before fluorine enters the silicon oxide.

In order for the transistor to have stable electrical characteristicswhich are close to normally-off characteristics, excess oxygen is set atadequate amounts.

<Heat Treatment>

Here, a method for controlling a furnace used for the heat treatment isdescribed with reference to FIGS. 75A to 75C. Note that an atmosphereused for the heat treatment described here is an example and can bechanged as appropriate.

FIG. 75A shows an example where heat treatment is performed twice indifferent atmospheres. First, an object is put in a furnace. Next, anitrogen gas is added into the furnace, and the temperature in thefurnace is set at a first temperature. The first temperature isincreased to a second temperature in an hour. The second temperature iskept for an hour. The second temperature is decreased to a thirdtemperature in an hour. Next, a nitrogen gas and an oxygen gas are addedinto the furnace. The third temperature is kept for an hour. The thirdtemperature is increased to a fourth temperature in an hour. The fourthtemperature is kept for an hour. The fourth temperature is decreased toa fifth temperature in an hour. Then, the object is taken out from thefurnace.

The first temperature, the third temperature, and the fifth temperatureare in a temperature range at which the object can be put in and takenout from the furnace (e.g., higher than or equal to 50° C. and lowerthan or equal to 200° C.). If the first temperature, the thirdtemperature, and the fifth temperature are too low, it takes a long timeto decrease the temperature, which might decline the productivity. Ifthe first temperature and the fifth temperature are too high, the objectmight be damaged when being put in or taken out from the furnace. Thesecond temperature and the fourth temperature are the maximumtemperatures of the heat treatment in the respective atmospheres (e.g.,higher than or equal to 250° C. and lower than or equal to 650° C.). Inthis specification, the time of heat treatment means the time duringwhich the maximum temperature is maintained in each atmosphere.

By the method shown in FIG. 75A, the total time is seven hours in thecase where two kinds of atmospheres are employed and each heat treatmentis performed for an hour.

FIG. 75B shows an example where heat treatment is performed once withoutchanging the atmosphere. First, an object is put in a furnace. Next,clean dry air (CDA) is added into the furnace, and the temperature inthe furnace is set at a sixth temperature. CDA is an air having a watercontent of less than or equal to 20 ppm, less than or equal to 1 ppm, orless than or equal to 10 ppb. The sixth temperature is increased to aseventh temperature in an hour. The seventh temperature is kept for twohours. The seventh temperature is decreased to an eighth temperature inan hour. Then, the object is taken out from the furnace.

The sixth temperature and the eighth temperature are in a temperaturerange at which the object can be put in and taken out from the furnace.The seventh temperature is the maximum temperature of the heat treatmentin the respective atmospheres.

By the method shown in FIG. 75B, the total time is four hours in thecase where one kind of atmosphere is employed and heat treatment isperformed for two hours.

FIG. 75C shows an example where heat treatment is performed once indifferent atmospheres. First, an object is put in a furnace. Next, anitrogen gas is added into the furnace, and the temperature in thefurnace is set at a ninth temperature. The ninth temperature isincreased to a tenth temperature in an hour. The tenth temperature iskept for an hour. Next, CDA is added into the furnace. The tenthtemperature is kept for an hour. The tenth temperature is decreased toan eleventh temperature in an hour. Then, the object is taken out fromthe furnace.

The ninth temperature and the eleventh temperature are in a temperaturerange at which the object can be put in and taken out from the furnace.The tenth temperature is the maximum temperature of the heat treatmentin the respective atmospheres.

By the method shown in FIG. 75C, the total time is four hours in thecase where two kinds of atmospheres are employed and heat treatment isperformed for two hours.

The time for the heat treatment by the methods shown in FIGS. 75B and75C can be shorter than that by the method shown in FIG. 75A. Thus,semiconductor devices can be manufactured with high productivity.

Next, a resist or the like is formed over the semiconductor andprocessing is performed using the resist or the like, whereby theinsulator 106 a and the semiconductor 106 b are formed (see FIGS. 17Eand 17F).

Next, heat treatment is preferably performed. The heat treatment canfurther reduce water and hydrogen in the insulator 105, the insulator103, and the insulator 104. In addition, the insulator 104 can containexcess oxygen in some cases. The heat treatment may be performed at atemperature higher than or equal to 250° C. and lower than or equal to650° C., preferably higher than or equal to 450° C. and lower than orequal to 600° C., further preferably higher than or equal to 520° C. andlower than or equal to 570° C. The heat treatment is performed in aninert gas atmosphere or an atmosphere containing an oxidizing gas at 10ppm or more, 1% or more, or 10% or more. The heat treatment may beperformed under a reduced pressure. Alternatively, the heat treatmentmay be performed in such a manner that heat treatment is performed in aninert gas atmosphere, and then another heat treatment is performed in anatmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or10% or more in order to compensate desorbed oxygen. The heat treatmentcan increase the crystallinity of the insulator to be the insulator 106a and the semiconductor 106 b and can remove impurities, such ashydrogen and water, for example. For the heat treatment, lamp heatingcan be performed with use of an RTA apparatus. Heat treatment with anRTA apparatus is effective for an improvement in productivity because itneeds short time as compared with the case of using a furnace.

Note that in the case where a semiconductor element layer is providedbelow the transistor 10, the heat treatment can be performed in arelatively low temperature range (e.g., higher than or equal to 350° C.and lower than or equal to 445° C.). For example, the temperature ispreferably set lower than or equal to the highest heating temperatureamong the substrate heating temperatures for forming the insulator 105,the insulator 103, and the insulator 104.

Next, the insulator 106 c is formed (see FIGS. 17G and 17H). Any of theabove-described insulators and semiconductors that can be used for theinsulator 106 c can be used for the insulator 106 c. The insulator 106 ccan be formed by a sputtering method, a CVD method, an MBE method, a PLDmethod, an ALD method, or the like.

Next, a conductor to be the conductor 108 a and the conductor 108 b isformed Any of the above-described conductors that can be used for theconductors 108 a and 108 b can be used for the conductor. The conductorcan be formed by a sputtering method, a CVD method, an MBE method, a PLDmethod, an ALD method, or the like.

Here, the low-resistance region 109 is formed in a region in thesemiconductor 106 b and the insulator 106 c near the conductor to be theconductor 108 in some cases.

Next, a resist or the like is formed over the conductor and processingis performed using the resist or the like, whereby the conductor 108 isformed.

Next, an insulator 113 that is to be the insulator 110 is formed. Any ofthe above-described insulators that can be used for the insulator 110can be used for the insulator 113, for example. The insulator 113 can beformed by a sputtering method, a CVD method, an MBE method, a PLDmethod, an ALD method, or the like.

When the insulator 113 is formed, part of top and side surfaces of theconductor 108 is oxidized to form the metal oxide 111 in some cases (seeFIGS. 18A and 18B).

Next, a resist or the like is formed over the insulator 113 andprocessing is performed using the resist or the like, whereby theinsulator 110, the metal oxide 111 a, the metal oxide 111 b, theconductor 108 a, and the conductor 108 b are formed (see FIGS. 18C and18D).

Next, high-density plasma treatment may be performed. The high-densityplasma treatment is preferably performed in an oxygen atmosphere. Theoxygen atmosphere is a gas atmosphere containing an oxygen atom andrefers to atmospheres of oxygen, ozone, and nitrogen oxide (e.g.,nitrogen monoxide, nitrogen dioxide, dinitrogen monoxide, dinitrogentrioxide, dinitrogen tetroxide, or dinitrogen pentoxide). In an oxygenatmosphere, an inert gas such as nitrogen or a rare gas (e.g., helium orargon) may be contained. With this high-density plasma treatmentperformed in an oxygen atmosphere, carbon or hydrogen can be eliminated,for example. Furthermore, with the high-density plasma treatment in anoxygen atmosphere, an organic compound such as hydrocarbon is alsoeasily eliminated from a treated object.

Annealing treatment may be performed before or after the high-densityplasma treatment. Note that it is in some cases preferable to let anenough amount of gas flow in order to increase the plasma density. Whenthe gas amount is not enough, the deactivation rate of radicals becomeshigher than the generation rate of radicals in some cases. For example,it is preferable in some cases to let a gas flow at 100 sccm or more,300 sccm or more, or 800 sccm or more.

The high-density plasma treatment is performed using a microwavegenerated with a high-frequency generator that generates a wave having afrequency of, for example, more than or equal to 0.3 GHz and less thanor equal to 3.0 GHz, more than or equal to 0.7 GHz and less than orequal to 1.1 GHz, or more than or equal to 2.2 GHz and less than orequal to 2.8 GHz (typically, 2.45 GHz). The treatment pressure can behigher than or equal to 10 Pa and lower than or equal to 5000 Pa,preferably higher than or equal to 200 Pa and lower than or equal to1500 Pa, further preferably higher than or equal to 300 Pa and lowerthan or equal to 1000 Pa. The substrate temperature can be higher thanor equal to 100° C. and lower than or equal to 600° C. (typically 400°C.). Furthermore, a mixed gas of oxygen and argon can be used.

For example, the high density plasma is generated using a 2.45 GHzmicrowave and preferably has an electron density of higher than or equalto 1×10¹¹/cm³ and lower than or equal to 1×10¹³/cm³, an electrontemperature of 2 eV or lower, or an ion energy of 5 eV or lower. Suchhigh-density plasma treatment produces radicals with low kinetic energyand causes little plasma damage, compared with conventional plasmatreatment. Thus, formation of a film with few defects is possible. Thedistance between an antenna that generates the microwave and the treatedobject is longer than or equal to 5 mm and shorter than or equal to 120mm, preferably longer than or equal to 20 mm and shorter than or equalto 60 mm.

Alternatively, a plasma power source that applies a radio frequency (RF)bias to a substrate may be provided. The frequency of the RF bias may be13.56 MHz, 27.12 MHz, or the like, for example. The use of high-densityplasma enables high-density oxygen ions to be produced, and applicationof the RF bias to the substrate allows oxygen ions generated by thehigh-density plasma to be efficiently introduced into the treatedobject. Furthermore, oxygen ions can be efficiently introduced even intoan opening with a high aspect ratio. Therefore, it is preferable toperform the high-density plasma treatment while a bias is applied to thesubstrate.

Following the high-density plasma treatment, annealing treatment may besuccessively performed without an exposure to the air. Followingannealing treatment, the high-density plasma treatment may besuccessively performed without an exposure to the air. By performinghigh-density plasma treatment and annealing treatment in succession,entry of impurities during the treatment can be suppressed. Moreover, byperforming annealing treatment after the high-density plasma treatmentin an oxygen atmosphere, unnecessary oxygen that is added into thetreated object but is not used to fill oxygen vacancies can beeliminated. The annealing treatment may be performed by lamp annealingor the like, for example.

The treatment time of the high-density plasma treatment is preferablylonger than or equal to 30 seconds and shorter than or equal to 120minutes, longer than or equal to 1 minute and shorter than or equal to90 minutes, longer than or equal to 2 minutes and shorter than or equalto 30 minutes, or longer than or equal to 3 minutes and shorter than orequal to 15 minutes.

The treatment time of the annealing treatment at a temperature of higherthan or equal to 250° C. and lower than or equal to 800° C., higher thanor equal to 300° C. and lower than or equal to 700° C., or higher thanor equal to 400° C. and lower than or equal to 600° C. is preferablylonger than or equal to 30 seconds and shorter than or equal to 120minutes, longer than or equal to 1 minute and shorter than or equal to90 minutes, longer than or equal to 2 minutes and shorter than or equalto 30 minutes, or longer than or equal to 3 minutes and shorter than orequal to 15 minutes.

By the high-density plasma treatment and/or the annealing treatment,defect states in a region of the semiconductor 106 b to be a channelformation region can be reduced. That is, the channel formation regioncan be a highly purified intrinsic region. At this time, the resistanceof part of the low-resistance region 109 is increased, so that thelow-resistance region 109 is divided into the low-resistance region 109a and the low-resistance region 109 b. The metal oxides 111 a and 111 bare formed on the side surfaces of the conductors 108 a and 108 b (seeFIGS. 18E and 18F).

Then, the insulator 132 is formed. Any of the above-described insulatorsthat can be used for the insulator 112 can be used for the insulator132. The insulator 132 can be formed by a sputtering method, a CVDmethod, an MBE method, a PLD method, an ALD method, or the like. Notethat successive film formation of the insulator 126 c and the insulator132 without exposure to the air can reduce entry of impurities into thefilms and their interface.

Next, the conductor 134 is formed (see FIGS. 19A and 19B). Any of theabove-described conductors that can be used for the conductor 114 can beused for the conductor 134. The conductor 134 can be formed by asputtering method, a CVD method, an MBE method, a PLD method, an ALDmethod, or the like. Note that successive film formation of theinsulator 132 and the conductor 134 without exposure to the air canreduce entry of impurities into the films and their interface.

Next, the conductor 134, the insulator 132, and the insulator 113 arepolished until the insulator 113 is exposed, whereby the conductor 114,the insulator 112, and the insulator 110 are formed (see FIGS. 19C and19D). The conductor 114 serves as a gate electrode of the transistor 29and the insulator 112 serves as a gate insulator of the transistor 29.As described above, the conductor 114 and the insulator 112 can beformed in a self-aligned manner.

Then, the insulator 116 is formed (see FIGS. 19E and 19F). Any of theabove-described insulators can be used for the insulator 116. Theinsulator 116 can be formed by a sputtering method, a CVD method, an MBEmethod, a PLD method, an ALD method, or the like.

Next, heat treatment is preferably performed.

Through the above process, the transistor of one embodiment of thepresent invention can be fabricated.

By the method for fabricating a transistor described in this embodiment,supply of water, hydrogen, and the like to the semiconductor 106 b canbe suppressed. As a result, a transistor with stable electricalcharacteristics can be provided. A transistor having a low leakagecurrent in an off state can be provided. A transistor with normally-offelectrical characteristics can be provided. A transistor with a smallsubthreshold swing value can be provided. A highly reliable transistorcan be provided.

In the method for forming a transistor described in this embodiment,supply of water, hydrogen, and the like to the semiconductor 106 b andthe like can be prevented by heat treatment within a relatively lowtemperature range; accordingly, even when a semiconductor element layer,a wiring layer, or the like is formed below the transistor, thetransistor can be formed without being degraded due to high temperature.

The structure and method described in this embodiment can be implementedby being combined as appropriate with any of the other structures andmethods described in the other embodiments.

Embodiment 3

<Manufacturing Apparatus>

A manufacturing apparatus of one embodiment of the present invention inwhich high-density plasma treatment is performed is described below.

First, a structure of a manufacturing apparatus which allows the entryof few impurities into a film at the time of formation of asemiconductor device or the like is described with reference to FIG. 20, FIG. 21 , and FIG. 22 .

FIG. 20 is a top view schematically illustrating a single wafermulti-chamber manufacturing apparatus 2700. The manufacturing apparatus2700 includes an atmosphere-side substrate supply chamber 2701 includinga cassette port 2761 for holding a substrate and an alignment port 2762for performing alignment of a substrate, an atmosphere-side substratetransfer chamber 2702 through which a substrate is transferred from theatmosphere-side substrate supply chamber 2701, a load lock chamber 2703a where a substrate is carried and the pressure inside the chamber isswitched from atmospheric pressure to reduced pressure or from reducedpressure to atmospheric pressure, an unload lock chamber 2703 b where asubstrate is carried out and the pressure inside the chamber is switchedfrom reduced pressure to atmospheric pressure or from atmosphericpressure to reduced pressure, a transfer chamber 2704 through which asubstrate is transferred in a vacuum, and chambers 2706 a, 2706 b, 2706c, and 2706 d.

The atmosphere-side substrate transfer chamber 2702 is connected to theload lock chamber 2703 a and the unload lock chamber 2703 b, the loadlock chamber 2703 a and the unload lock chamber 2703 b are connected tothe transfer chamber 2704, and the transfer chamber 2704 is connected tothe chambers 2706 a, 2706 b, 2706 c, and 2706 d.

Note that gate valves GV are provided in connecting portions between thechambers so that each chamber excluding the atmosphere-side substratesupply chamber 2701 and the atmosphere-side substrate transfer chamber2702 can be independently kept in a vacuum state. In addition, theatmosphere-side substrate transfer chamber 2702 is provided with atransfer robot 2763 a, and the transfer chamber 2704 is provided with atransfer robot 2763 b. With the transfer robot 2763 a and the transferrobot 2763 b, a substrate can be transferred inside the manufacturingapparatus 2700.

In the transfer chamber 2704 and each of the chambers 2706 a to 2706 d,the back pressure (total pressure) is, for example, lower than or equalto 1×10⁻⁴ Pa, preferably lower than or equal to 3×10⁻⁵ Pa, furtherpreferably lower than or equal to 1×10⁻⁵ Pa. In the transfer chamber2704 and each of the chambers 2706 a to 2706 d, the partial pressure ofa gas molecule (atom) having a mass-to-charge ratio (m/z) of 18 is, forexample, lower than or equal to 3×10⁻⁵ Pa, preferably lower than orequal to 1×10⁻⁵ Pa, further preferably lower than or equal to 3×10⁻⁶ Pa.Moreover, in the transfer chamber 2704 and each of the chambers 2706 ato 2706 d, the partial pressure of a gas molecule (atom) having amass-to-charge ratio (m/z) of 28 is, for example, lower than or equal to3×10⁻⁵ Pa, preferably lower than or equal to 1×10⁻⁵ Pa, furtherpreferably lower than or equal to 3×10⁻⁶ Pa. Further, in the transferchamber 2704 and each of the chambers 2706 a to 2706 d, the partialpressure of a gas molecule (atom) having a mass-to-charge ratio (m/z) of44 is, for example, lower than or equal to 3×10⁻⁵ Pa, preferably lowerthan or equal to 1×10⁻⁵ Pa, further preferably lower than or equal to3×10⁻⁶ Pa.

Note that the total pressure and the partial pressure in the transferchamber 2704 and each of the chambers 2706 a to 2706 d can be measuredusing a mass analyzer. For example, Qulee CGM-051, a quadrupole massanalyzer (also referred to as Q-mass) manufactured by ULVAC, Inc. can beused.

Moreover, the transfer chamber 2704 and each of the chambers 2706 a to2706 d preferably have a small amount of external leakage or internalleakage. For example, in the transfer chamber 2704 and each of thechambers 2706 a to 2706 d, the leakage rate is less than or equal to3×10⁻⁶ Pa·m³/s, preferably less than or equal to 1×10⁻⁶ Pa·m³/s. Forexample, the leakage rate of a gas molecule (atom) having amass-to-charge ratio (m/z) of 18 is less than or equal to 1×10⁻⁷Pa·m³/s, preferably less than or equal to 3×10⁻⁸ Pa·m³/s. For example,the leakage rate of a gas molecule (atom) having a mass-to-charge ratio(m/z) of 28 is less than or equal to 1×10⁻⁵ Pa·m³/s, preferably lessthan or equal to 1×10⁻⁶ Pa·m³/s. For example, the leakage rate of a gasmolecule (atom) having a mass-to-charge ratio (m/z) of 44 is less thanor equal to 3×10⁻⁶ Pa·m³/s, preferably less than or equal to 1×10⁻⁶Pa·m³/s.

Note that a leakage rate can be derived from the total pressure andpartial pressure measured using the mass analyzer. The leakage ratedepends on external leakage and internal leakage. The external leakagerefers to inflow of gas from the outside of a vacuum system through aminute hole, a sealing defect, or the like. The internal leakage is dueto leakage through a partition, such as a valve, in a vacuum system ordue to released gas from an internal member. Measures need to be takenfrom both aspects of external leakage and internal leakage in order thatthe leakage rate can be set to be less than or equal to theabove-mentioned value.

For example, open/close portions of the transfer chamber 2704 and thechambers 2706 a to 2706 d can be sealed with a metal gasket. For themetal gasket, metal covered with iron fluoride, aluminum oxide, orchromium oxide is preferably used. The metal gasket realizes higheradhesion than an O-ring, and can reduce the external leakage.

Furthermore, with the use of the metal covered with iron fluoride,aluminum oxide, chromium oxide, or the like, which is in the passivestate, the release of gas containing impurities released from the metalgasket is suppressed, so that the internal leakage can be reduced.

For a member of the manufacturing apparatus 2700, aluminum, chromium,titanium, zirconium, nickel, or vanadium, which releases a small amountof gas containing impurities, is used. Alternatively, an alloycontaining iron, chromium, nickel, or the like covered with the abovematerial may be used. The alloy containing iron, chromium, nickel, orthe like is rigid, resistant to heat, and suitable for processing. Here,when surface unevenness of the member is decreased by polishing or thelike to reduce the surface area, the release of gas can be reduced.

Alternatively, the above member of the manufacturing apparatus 2700 maybe covered with iron fluoride, aluminum oxide, chromium oxide, or thelike.

The member of the manufacturing apparatus 2700 is preferably formedusing only metal when possible. For example, in the case where a viewingwindow formed of quartz or the like is provided, it is preferable thatthe surface of the viewing window be thinly covered with iron fluoride,aluminum oxide, chromium oxide, or the like so as to suppress release ofgas.

When an adsorbed substance is present in the transfer chamber 2704 andeach of the chambers 2706 a to 2706 d, although the adsorbed substancedoes not affect the pressure in the transfer chamber 2704 and each ofthe chambers 2706 a to 2706 d because it is adsorbed onto an inner wallor the like, the adsorbed substance causes a release of gas when theinside of the transfer chamber 2704 and each of the chambers 2706 a to2706 d is evacuated. Therefore, although there is no correlation betweenthe leakage rate and the exhaust rate, it is important that the adsorbedsubstance present in the transfer chamber 2704 and each of the chambers2706 a to 2706 d be desorbed as much as possible and exhaust beperformed in advance with the use of a pump with high exhaustcapability. Note that the transfer chamber 2704 and each of the chambers2706 a to 2706 d may be subjected to baking to promote desorption of theadsorbed substance. By the baking, the desorption rate of the adsorbedsubstance can be increased about tenfold. The baking can be performed ata temperature of higher than or equal to 100° C. and lower than or equalto 450° C. At this time, when the adsorbed substance is removed while aninert gas is introduced into the transfer chamber 2704 and each of thechambers 2706 a to 2706 d, the desorption rate of water or the like,which is difficult to desorb simply by exhaust, can be furtherincreased. Note that when the inert gas that is introduced is heated tosubstantially the same temperature as the baking temperature, thedesorption rate of the adsorbed substance can be further increased.Here, a rare gas is preferably used as the inert gas.

Alternatively, treatment for evacuating the inside of the transferchamber 2704 and each of the chambers 2706 a to 2706 d is preferablyperformed a certain period of time after heated oxygen, a heated inertgas such as a heated rare gas, or the like is introduced to increase thepressure in the transfer chamber 2704 and each of the chambers 2706 a to2706 d. The introduction of the heated gas can desorb the adsorbedsubstance in the transfer chamber 2704 and each of the chambers 2706 ato 2706 d, and the impurities present in the transfer chamber 2704 andeach of the chambers 2706 a to 2706 d can be reduced. Note that anadvantageous effect can be achieved when this treatment is repeated morethan or equal to 2 times and less than or equal to 30 times, preferablymore than or equal to 5 times and less than or equal to 15 times.Specifically, an inert gas, oxygen, or the like with a temperaturehigher than or equal to 40° C. and lower than or equal to 400° C.,preferably higher than or equal to 50° C. and lower than or equal to200° C. is introduced to the transfer chamber 2704 and each of thechambers 2706 a to 2706 d, so that the pressure therein can be kept tobe higher than or equal to 0.1 Pa and lower than or equal to 10 kPa,preferably higher than or equal to 1 Pa and lower than or equal to 1kPa, further preferably higher than or equal to 5 Pa and lower than orequal to 100 Pa in the time range of 1 minute to 300 minutes, preferably5 minutes to 120 minutes. After that, the inside of the transfer chamber2704 and each of the chambers 2706 a to 2706 d is evacuated in the timerange of 5 minutes to 300 minutes, preferably 10 minutes to 120 minutes.

Next, the chambers 2706 b and 2706 c are described with reference to aschematic cross-sectional view of FIG. 21 .

The chambers 2706 b and 2706 c are chambers capable of performinghigh-density plasma treatment on an object, for example. Because thechambers 2706 b and 2706 c have a common structure with the exception ofthe atmosphere used in the high-density plasma treatment, they arecollectively described below.

The chambers 2706 b and 2706 c each include a slot antenna plate 2808, adielectric plate 2809, a substrate stage 2812, and an exhaust port 2819.A gas supply source 2801, a valve 2802, a high-frequency generator 2803,a waveguide 2804, a mode converter 2805, a gas pipe 2806, a waveguide2807, a matching box 2815, a high-frequency power source 2816, a vacuumpump 2817, and a valve 2818 are provided outside the chambers 2706 b and2706 c.

The high-frequency generator 2803 is connected to the mode converter2805 through the waveguide 2804. The mode converter 2805 is connected tothe slot antenna plate 2808 through the waveguide 2807. The slot antennaplate 2808 is positioned in contact with the dielectric plate 2809.Further, the gas supply source 2801 is connected to the mode converter2805 through the valve 2802. Gas is transferred to the chambers 2706 band 2706 c through the gas pipe 2806 which runs through the modeconverter 2805, the waveguide 2807, and the dielectric plate 2809. Thevacuum pump 2817 has a function of exhausting gas or the like from thechambers 2706 b and 2706 c through the valve 2818 and the exhaust port2819. The high-frequency power source 2816 is connected to the substratestage 2812 through the matching box 2815.

The substrate stage 2812 has a function of holding a substrate 2811. Forexample, the substrate stage 2812 has a function of an electrostaticchuck or a mechanical chuck for holding the substrate 2811. In addition,the substrate stage 2812 has a function of an electrode to whichelectric power is supplied from the high-frequency power source 2816.The substrate stage 2812 includes a heating mechanism 2813 therein andthus has a function of heating the substrate 2811.

As the vacuum pump 2817, a dry pump, a mechanical booster pump, an ionpump, a titanium sublimation pump, a cryopump, a turbomolecular pump, orthe like can be used, for example. In addition to the vacuum pump 2817,a cryotrap may be used as well. The combinational use of the cryopumpand the cryotrap allows water to be efficiently exhausted and isparticularly preferable.

For example, the heating mechanism 2813 may be a heating mechanism whichuses a resistance heater or the like for heating. Alternatively, aheating mechanism which utilizes heat conduction or heat radiation froma medium such as a heated gas for heating may be used. For example,rapid thermal annealing (RTA) such as gas rapid thermal annealing (GRTA)or lamp rapid thermal annealing (LRTA) can be used. In GRTA, heattreatment is performed using a high-temperature gas. An inert gas isused as the gas.

The gas supply source 2801 may be connected to a purifier through a massflow controller. As the gas, a gas whose dew point is −80° C. or lower,preferably −100° C. or lower is preferably used. For example, an oxygengas, a nitrogen gas, or a rare gas (e.g., an argon gas) may be used.

As the dielectric plate 2809, silicon oxide (quartz), aluminum oxide(alumina), yttrium oxide (yttria), or the like may be used, for example.A protective layer may be further formed on a surface of the dielectricplate 2809. As the protective layer, magnesium oxide, titanium oxide,chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, siliconoxide, aluminum oxide, yttrium oxide, or the like may be used. Thedielectric plate 2809 is exposed to an especially high density region ofhigh-density plasma 2810 that is to be described later. Therefore, theprotective layer can reduce the damage and consequently prevent anincrease of particles or the like during the treatment.

The high-frequency generator 2803 has a function of generating amicrowave with a frequency of, for example, more than or equal to 0.3GHz and less than or equal to 3.0 GHz, more than or equal to 0.7 GHz andless than or equal to 1.1 GHz, or more than or equal to 2.2 GHz and lessthan or equal to 2.8 GHz. The microwave generated by the high-frequencygenerator 2803 is propagated to the mode converter 2805 through thewaveguide 2804. The mode converter 2805 converts the microwavepropagated in the TE mode into a microwave in the TEM mode. Then, themicrowave is propagated to the slot antenna plate 2808 through thewaveguide 2807. The slot antenna plate 2808 is provided with a pluralityof slot holes, and the microwave propagates through the slot holes andthe dielectric plate 2809. Then, an electric field is generated belowthe dielectric plate 2809, and the high-density plasma 2810 can begenerated. The high-density plasma 2810 includes ions and radicalsdepending on the gas species supplied from the gas supply source 2801.For example, oxygen radicals, nitrogen radicals, or the like areincluded.

At this time, the quality of a film or the like over the substrate 2811can be modified by the ions and radicals generated in the high-densityplasma 2810. Note that it is preferable in some cases to apply a bias tothe substrate 2811 using the high-frequency power source 2816. As thehigh-frequency power source 2816, a radio frequency (RF) power sourcewith a frequency of 13.56 MHz, 27.12 MHz, or the like may be used, forexample. The application of a bias to the substrate allows ions in thehigh-density plasma 2810 to efficiently reach a deep portion of anopening of the film or the like over the substrate 2811.

For example, in the chamber 2706 b, oxygen radical treatment using thehigh-density plasma 2810 can be performed by introducing oxygen from thegas supply source 2801. In the chamber 2706 c, nitrogen radicaltreatment using the high-density plasma 2810 can be performed byintroducing nitrogen from the gas supply source 2801.

Next, the chambers 2706 a and 2706 d are described with reference to aschematic cross-sectional view of FIG. 22 .

The chambers 2706 a and 2706 d are chambers capable of irradiating anobject with an electromagnetic wave, for example. Because the chambers2706 a and 2706 d have a common structure with the exception of the kindof the electromagnetic wave, they are collectively described below.

The chambers 2706 a and 2706 d each include one or more lamps 2820, asubstrate stage 2825, a gas inlet 2823, and an exhaust port 2830. A gassupply source 2821, a valve 2822, a vacuum pump 2828, and a valve 2829are provided outside the chambers 2706 a and 2706 d.

The gas supply source 2821 is connected to the gas inlet 2823 throughthe valve 2822. The vacuum pump 2828 is connected to the exhaust port2830 through the valve 2829. The lamp 2820 is provided to face thesubstrate stage 2825. The substrate stage 2825 has a function of holdinga substrate 2824. The substrate stage 2825 includes a heating mechanism2826 therein and thus has a function of heating the substrate 2824.

As the lamp 2820, a light source having a function of emitting anelectromagnetic wave such as visible light or ultraviolet light may beused, for example. For example, a light source having a function ofemitting an electromagnetic wave which has a peak in a wavelength regionof longer than or equal to 10 nm and shorter than or equal to 2500 nm,longer than or equal to 500 nm and shorter than or equal to 2000 nm, orlonger than or equal to 40 nm and shorter than or equal to 340 nm may beused.

As the lamp 2820, a light source such as a halogen lamp, a metal halidelamp, a xenon arc lamp, a carbon arc lamp, a high-pressure sodium lamp,or a high-pressure mercury lamp may be used, for example.

For example, part of or the whole electromagnetic wave emitted from thelamp 2820 is absorbed by the substrate 2824, so that the quality of afilm or the like over the substrate 2824 can be modified. For example,defects can be generated or reduced or impurities can be removed. Whenthe substrate 2824 absorbs the electromagnetic wave while being heated,generation or reduction of defects or removal of impurities can beefficiently performed.

Alternatively, for example, the electromagnetic wave emitted from thelamp 2820 may cause heat generation in the substrate stage 2825, bywhich the substrate 2824 may be heated. In this case, the heatingmechanism 2826 inside the substrate stage 2825 may be omitted.

For the vacuum pump 2828, the description of the vacuum pump 2817 isreferred to. For the heating mechanism 2826, the description of theheating mechanism 2813 is referred to. For the gas supply source 2821,the description of the gas supply source 2801 is referred to.

With the above-described manufacturing apparatus, the quality of a filmcan be modified while the entry of impurities into an object suppressed.

The structure and method described in this embodiment can be implementedby being combined as appropriate with any of the other structures andmethods described in the other embodiments.

Embodiment 4

In this embodiment, an example of a circuit of a semiconductor deviceincluding a transistor or the like of one embodiment of the presentinvention is described.

<Circuit>

An example of a circuit of a semiconductor device including a transistoror the like of one embodiment of the present invention is describedbelow.

<CMOS Inverter>

A circuit diagram in FIG. 23A shows a configuration of what is called aCMOS inverter in which a p-channel transistor 2200 and an n-channeltransistor 2100 are connected to each other in series and in which gatesof them are connected to each other.

<Structure of Semiconductor Device>

FIG. 24 is a cross-sectional view of the semiconductor device of FIG.23A. The semiconductor device shown in FIG. 24 includes the transistor2200 and the transistor 2100. The transistor 2100 is placed above thetransistor 2200. Note that an example where the transistor 20 shown inFIGS. 9A and 9B is used as the transistor 2100 is shown, but asemiconductor device of one embodiment of the present invention is notlimited thereto. Any of the transistors described in the aboveembodiments can be used as the transistor 2100. Therefore, thedescription regarding the above-mentioned transistors is referred to forthe transistor 2100 as appropriate.

The transistor 2200 shown in FIG. 24 is a transistor using asemiconductor substrate 450. The transistor 2200 includes a region 472 ain the semiconductor substrate 450, a region 472 b in the semiconductorsubstrate 450, an insulator 462, and a conductor 454.

In the transistor 2200, the regions 472 a and 472 b have functions of asource region and a drain region. The insulator 462 serves as a gateinsulator. The conductor 454 serves as a gate electrode. Thus, theresistance of a channel formation region can be controlled by apotential applied to the conductor 454. In other words, conduction ornon-conduction between the region 472 a and the region 472 b can becontrolled by the potential applied to the conductor 454.

For the semiconductor substrate 450, a single-material semiconductorsubstrate formed using silicon, germanium, or the like or asemiconductor substrate formed using silicon carbide, silicon germanium,gallium arsenide, indium phosphide, zinc oxide, gallium oxide, or thelike may be used, for example. A single crystal silicon substrate ispreferably used as the semiconductor substrate 450.

For the semiconductor substrate 450, a semiconductor substrate includingimpurities imparting n-type conductivity is used. However, asemiconductor substrate including impurities imparting p-typeconductivity may be used as the semiconductor substrate 450. In thatcase, a well including impurities imparting the n-type conductivity maybe provided in a region where the transistor 2200 is formed.Alternatively, the semiconductor substrate 450 may be an i-typesemiconductor substrate.

The top surface of the semiconductor substrate 450 preferably has a(110) plane. Thus, on-state characteristics of the transistor 2200 canbe improved.

The regions 472 a and 472 b are regions including impurities impartingthe p-type conductivity. Accordingly, the transistor 2200 has astructure of a p-channel transistor.

Note that the transistor 2200 is apart from an adjacent transistor by aregion 460 and the like. The region 460 is an insulating region.

The semiconductor device illustrated in FIG. 24 includes an insulator464, an insulator 466, an insulator 468, a conductor 480 a, a conductor480 b, a conductor 480 c, a conductor 478 a, a conductor 478 b, aconductor 478 c, a conductor 476 a, a conductor 476 b, a conductor 474a, a conductor 474 b, a conductor 474 c, a conductor 496 a, a conductor496 b, a conductor 496 c, a conductor 496 d, a conductor 498 a, aconductor 498 b, a conductor 498 c, an insulator 489, an insulator 490,an insulator 491, an insulator 492, an insulator 493, and an insulator494.

The insulator 464 is placed over the transistor 2200. The insulator 466is placed over the insulator 464. The insulator 468 is placed over theinsulator 466. The insulator 489 is placed over the insulator 468. Thetransistor 2100 is placed over the insulator 489. The insulator 493 isplaced over the transistor 2100. The insulator 494 is placed over theinsulator 493.

The insulator 464 includes an opening reaching the region 472 a, anopening reaching the region 472 b, and an opening reaching the conductor454. In the openings, the conductor 480 a, the conductor 480 b, and theconductor 480 c are embedded.

The insulator 466 includes an opening reaching the conductor 480 a, anopening reaching the conductor 480 b, and an opening reaching theconductor 480 c. In the openings, the conductor 478 a, the conductor 478b, and the conductor 478 c are embedded.

The insulator 468 includes an opening reaching the conductor 478 b andan opening reaching the conductor 478 c. In the openings, the conductor476 a and the conductor 476 b are embedded.

The insulator 489 includes an opening overlapping with a channelformation region of the transistor 2100, an opening reaching theconductor 476 a, and an opening reaching the conductor 476 b. In theopenings, the conductor 474 a, the conductor 474 b, and the conductor474 c are embedded.

The conductor 474 a may serve as a gate electrode of the transistor2100. The electrical characteristics of the transistor 2100, such as thethreshold voltage, may be controlled by application of a predeterminedpotential to the conductor 474 a, for example. The conductor 474 a maybe electrically connected to the conductor 504 having a function of thegate electrode of the transistor 2100, for example. In that case,on-state current of the transistor 2100 can be increased. Furthermore, apunch-through phenomenon can be suppressed; thus, the electricalcharacteristics of the transistor 2100 in a saturation region can bestable. Note that the conductor 474 a corresponds to the conductor 102in the above embodiment and thus, the description of the conductor 102can be referred to for details about the conductor 474 a.

The insulator 490 includes an opening reaching the conductor 474 b andan opening reaching the conductor 474 c. Note that the insulator 490corresponds to the insulator 103 in the above embodiment and thus, thedescription of the insulator 103 can be referred to for details aboutthe insulator 490. As described in the above embodiment, the insulator490 is provided to cover the conductors 474 a to 474 c except for theopenings, whereby extraction of oxygen from the insulator 491 by theconductors 474 a to 474 c can be prevented. Accordingly, oxygen can beeffectively supplied from the insulator 491 to an oxide semiconductor ofthe transistor 2100.

The insulator 491 includes the opening reaching the conductor 474 b andthe opening reaching the conductor 474 c. Note that the insulator 491corresponds to the insulator 104 in the above embodiment and thus, thedescription of the insulator 104 can be referred to for details aboutthe insulator 491.

As described in the above embodiment, the amounts of water and hydrogenin the insulator 491 can be reduced, so that defect states can beprevented from being formed in the oxide semiconductor of the transistor2100. Accordingly, the electrical characteristics of the transistor 2100can be stabilized.

Such an insulator in which water and hydrogen are reduced may be used asan insulator other than the insulator 491, such as the insulator 466,the insulator 468, the insulator 489, or the insulator 493.

Although insulators that correspond to the insulators 105 and 101 in thetransistor are not illustrated in FIG. 24 , these insulators may beprovided. For example, an insulator that corresponds to the insulator101 may be provided between the insulator 468 and the insulator 489, andan insulator that corresponds to the insulator 105 may be providedbetween the insulator 489 and the insulator 490. In particular, theinsulator that has a function of blocking water, hydrogen, and the likeand corresponds to the insulator 101 may be provided between theinsulator 468 and the insulator 489 and the amounts of water andhydrogen in the insulator 491 are reduced in the above-described manner,whereby defect states can be further prevented from being formed in theoxide semiconductor of the transistor 2100.

The insulator 492 includes an opening reaching the conductor 474 bthrough the conductor 516 b that is one of a source electrode and adrain electrode of the transistor 2100, an opening reaching theconductor 516 a that is the other of the source electrode and the drainelectrode of the transistor 2100, an opening reaching the conductor 504that is the gate electrode of the transistor 2100, and an openingreaching the conductor 474 c. Note that the insulator 492 corresponds tothe insulator 116 in the above embodiment and thus, the description ofthe insulator 116 can be referred to for details about the insulator492.

The insulator 493 includes an opening reaching the conductor 474 bthrough the conductor 516 b that is one of a source electrode and adrain electrode of the transistor 2100, an opening reaching theconductor 516 a that is the other of the source electrode and the drainelectrode of the transistor 2100, an opening reaching the conductor 504that is the gate electrode of the transistor 2100, and an openingreaching the conductor 474 c. In the openings, the conductor 496 a, theconductor 496 b, the conductor 496 c, and the conductor 496 d areembedded. Note that in some cases, an opening provided in a component ofthe transistor 2100 or the like is positioned between openings providedin other components.

The insulator 494 includes an opening reaching the conductor 496 a, anopening reaching the conductor 496 b and the conductor 496 d, and anopening reaching the conductor 496 c. In the openings, the conductor 498a, the conductor 498 b, and the conductor 498 c are embedded.

The insulators 464, 466, 468, 489, 493, and 494 may each be formed tohave, for example, a single-layer structure or a stacked-layer structureincluding an insulator containing boron, carbon, nitrogen, oxygen,fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon,gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium,or tantalum.

The insulator that has a function of blocking oxygen and impurities suchas hydrogen is preferably included in at least one of the insulators464, 466, 468, 489, 493, and 494. When an insulator that has a functionof blocking oxygen and impurities such as hydrogen is placed near thetransistor 2100, the electrical characteristics of the transistor 2100can be stable.

An insulator with a function of blocking oxygen and impurities such ashydrogen may be formed to have a single-layer structure or astacked-layer structure including an insulator containing, for example,boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon,phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium,lanthanum, neodymium, hafnium, or tantalum.

Each of the conductor 480 a, the conductor 480 b, the conductor 480 c,the conductor 478 a, the conductor 478 b, the conductor 478 c, theconductor 476 a, the conductor 476 b, the conductor 474 a, the conductor474 b, the conductor 474 c, the conductor 496 a, the conductor 496 b,the conductor 496 c, the conductor 496 d, the conductor 498 a, theconductor 498 b, and the conductor 498 c may be formed to have, forexample, a single-layer structure or a stacked-layer structure includinga conductor containing one or more kinds selected from boron, nitrogen,oxygen, fluorine, silicon, phosphorus, aluminum, titanium, chromium,manganese, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium,molybdenum, ruthenium, silver, indium, tin, tantalum, and tungsten. Analloy or a compound containing the above element may be used, forexample, and a conductor containing aluminum, a conductor containingcopper and titanium, a conductor containing copper and manganese, aconductor containing indium, tin, and oxygen, a conductor containingtitanium and nitrogen, or the like may be used.

Note that a semiconductor device in FIG. 25 is the same as thesemiconductor device in FIG. 24 except for the structure of thetransistor 2200. Therefore, the description of the semiconductor devicein FIG. 24 is referred to for the semiconductor device in FIG. 25 . Inthe semiconductor device in FIG. 25 , the transistor 2200 is a Fin-typetransistor. The effective channel width is increased in the Fin-typetransistor 2200, whereby the on-state characteristics of the transistor2200 can be improved. In addition, since contribution of the electricfield of the gate electrode can be increased, the off-statecharacteristics of the transistor 2200 can be improved.

Note that a semiconductor device in FIG. 26 is the same as thesemiconductor device in FIG. 24 except for the structure of thetransistor 2200. Therefore, the description of the semiconductor devicein FIG. 26 is referred to for the semiconductor device in FIG. 24 .Specifically, in the semiconductor device in FIG. 26 , the transistor2200 is formed in the semiconductor substrate 450 that is an SOIsubstrate. In the structure in FIG. 26 , a region 456 is apart from thesemiconductor substrate 450 with an insulator 452 provided therebetween.Since the SOI substrate is used as the semiconductor substrate 450, apunch-through phenomenon and the like can be suppressed; thus, theoff-state characteristics of the transistor 2200 can be improved. Notethat the insulator 452 can be formed by turning the semiconductorsubstrate 450 into an insulator. For example, silicon oxide can be usedas the insulator 452.

In each of the semiconductor devices shown in FIG. 24 to FIG. 26 , ap-channel transistor is formed utilizing a semiconductor substrate, andan n-channel transistor is formed above that; therefore, an occupationarea of the element can be reduced. That is, the integration degree ofthe semiconductor device can be improved. In addition, the manufacturingprocess can be simplified compared to the case where an n-channeltransistor and a p-channel transistor are formed utilizing the samesemiconductor substrate; therefore, the productivity of thesemiconductor device can be increased.

Moreover, the yield of the semiconductor device can be improved. For thep-channel transistor, some complicated steps such as formation oflightly doped drain (LDD) regions, formation of a shallow trenchstructure, or distortion design can be omitted in some cases. Therefore,the productivity and yield of the semiconductor device can be increasedin some cases, compared to a semiconductor device where an n-channeltransistor is formed utilizing the semiconductor substrate.

<CMOS Analog Switch>

A circuit diagram in FIG. 23B shows a configuration in which sources ofthe transistors 2100 and 2200 are connected to each other and drains ofthe transistors 2100 and 2200 are connected to each other. With such aconfiguration, the transistors can function as what is called a CMOSanalog switch.

<Memory Device 1>

An example of a semiconductor device (memory device) which includes thetransistor of one embodiment of the present invention, which can retainstored data even when not powered, and which has an unlimited number ofwrite cycles is shown in FIGS. 27A to 27C.

The semiconductor device illustrated in FIG. 27A includes a transistor3200 using a first semiconductor, a transistor 3300 using a secondsemiconductor, and a capacitor 3400. Note that a transistor similar tothe transistor 2100 can be used as the transistor 3300.

Note that the transistor 3300 is preferably a transistor with a lowoff-state current. For example, a transistor using an oxidesemiconductor can be used as the transistor 3300. Since the off-statecurrent of the transistor 3300 is low, stored data can be retained for along period at a predetermined node of the semiconductor device. Inother words, power consumption of the semiconductor device can bereduced because refresh operation becomes unnecessary or the frequencyof refresh operation can be extremely low.

In FIG. 27A, a first wiring 3001 is electrically connected to a sourceof the transistor 3200. A second wiring 3002 is electrically connectedto a drain of the transistor 3200. A third wiring 3003 is electricallyconnected to one of a source and a drain of the transistor 3300. Afourth wiring 3004 is electrically connected to a gate of the transistor3300. A gate of the transistor 3200 and the other of the source and thedrain of the transistor 3300 are electrically connected to one electrodeof the capacitor 3400. A fifth wiring 3005 is electrically connected tothe other electrode of the capacitor 3400.

The semiconductor device in FIG. 27A has a feature that the potential ofthe gate of the transistor 3200 can be retained, and thus enableswriting, retaining, and reading of data as follows.

Writing and retaining of data are described. First, the potential of thefourth wiring 3004 is set to a potential at which the transistor 3300 ison, so that the transistor 3300 is turned on. Accordingly, the potentialof the third wiring 3003 is supplied to a node FG where the gate of thetransistor 3200 and the one electrode of the capacitor 3400 areelectrically connected to each other. That is, a predetermined electriccharge is supplied to the gate of the transistor 3200 (writing). Here,one of two kinds of electric charges providing different potentiallevels (hereinafter referred to as a low-level electric charge and ahigh-level electric charge) is supplied. After that, the potential ofthe fourth wiring 3004 is set to a potential at which the transistor3300 is off, so that the transistor 3300 is turned off. Thus, theelectric charge is held at the node FG (retaining).

Since the off-state current of the transistor 3300 is low, the electriccharge of the node FG is retained for a long time.

Next, reading of data is described. An appropriate potential (a readingpotential) is supplied to the fifth wiring 3005 while a predeterminedpotential (a constant potential) is supplied to the first wiring 3001,whereby the potential of the second wiring 3002 varies depending on theamount of electric charge retained in the node FG. This is because inthe case of using an n-channel transistor as the transistor 3200, anapparent threshold voltage V_(th_H) at the time when the high-levelelectric charge is given to the gate of the transistor 3200 is lowerthan an apparent threshold voltage V_(th_L) at the time when thelow-level electric charge is given to the gate of the transistor 3200.Here, an apparent threshold voltage refers to the potential of the fifthwiring 3005 which is needed to make the transistor 3200 be in “onstate.” Thus, the potential of the fifth wiring 3005 is set to apotential V₀ which is between V_(th_H) and V_(th_L), whereby electriccharge supplied to the node FG can be determined. For example, in thecase where the high-level electric charge is supplied to the node FG inwriting and the potential of the fifth wiring 3005 is V₀ (>V_(th_H)),the transistor 3200 is brought into “on state.” In the case where thelow-level electric charge is supplied to the node FG in writing, evenwhen the potential of the fifth wiring 3005 is V₀ (<V_(th_L)), thetransistor 3200 still remains in “off state.” Thus, the data retained inthe node FG can be read by determining the potential of the secondwiring 3002.

Note that in the case where memory cells are arrayed, it is necessarythat data of a desired memory cell be read in read operation. Forexample, a configuration in which only data of a desired memory cell canbe read by supplying a potential at which the transistor 3200 is broughtinto an “off state” regardless of the charge supplied to the node FG,that is, a potential lower than V_(th_H) to the fifth wiring 3005 ofmemory cells from which data is not read may be employed. Alternatively,a configuration in which only data of a desired memory cell can be readby supplying a potential at which the transistor 3200 is brought into an“on state” regardless of the charge supplied to the node FG, that is, apotential higher than V_(th_L) to the fifth wiring 3005 of memory cellsfrom which data is not read may be employed.

Although an example in which two kinds of electric charges are retainedin the node FG, the semiconductor device of the present invention is notlimited to this example. For example, a structure in which three or morekinds of electric charges can be retained in the node FG of thesemiconductor device may be employed. With such a structure, thesemiconductor device can be multi-valued and the storage capacity can beincreased.

<Structure of Memory Device 1>

FIG. 28 is a cross-sectional view of the semiconductor device of FIG.27A. The semiconductor device shown in FIG. 28 includes the transistor3200, the transistor 3300, and the capacitor 3400. The transistor 3300and the capacitor 3400 are placed above the transistor 3200. Note thatfor the transistor 3300, the description of the above transistor 2100 isreferred to. Furthermore, for the transistor 3200, the description ofthe transistor 2200 in FIG. 24 is referred to. Note that although thetransistor 2200 is illustrated as a p-channel transistor in FIG. 24 ,the transistor 3200 may be an n-channel transistor.

The transistor 3200 illustrated in FIG. 28 is a transistor using thesemiconductor substrate 450. The transistor 3200 includes the region 472a in the semiconductor substrate 450, the region 472 b in thesemiconductor substrate 450, the insulator 462, and the conductor 454.

The semiconductor device illustrated in FIG. 28 includes the insulator464, the insulator 466, the insulator 468, the conductor 480 a, theconductor 480 b, the conductor 480 c, the conductor 478 a, the conductor478 b, the conductor 478 c, the conductor 476 a, the conductor 476 b,the conductor 474 a, the conductor 474 b, the conductor 474 c, theconductor 496 a, the conductor 496 b, the conductor 496 c, the conductor496 d, the conductor 498 a, the conductor 498 b, the conductor 498 c,the insulator 489, the insulator 490, the insulator 491, the insulator492, the insulator 493, and the insulator 494.

The insulator 464 is provided over the transistor 3200. The insulator466 is provided over the insulator 464. The insulator 468 is providedover the insulator 466. The insulator 489 is provided over the insulator468. The transistor 3300 is provided over the insulator 489. Theinsulator 493 is provided over the transistor 3300. The insulator 494 isprovided over the insulator 493.

The insulator 464 has an opening reaching the region 472 a, an openingreaching the region 472 b, and an opening reaching the conductor 454. Inthe openings, the conductor 480 a, the conductor 480 b, and theconductor 480 c are embedded.

The insulator 466 includes an opening reaching the conductor 480 a, anopening reaching the conductor 480 b, and an opening reaching theconductor 480 c. In the openings, the conductor 478 a, the conductor 478b, and the conductor 478 c are embedded.

The insulator 468 includes an opening reaching the conductor 478 b andan opening reaching the conductor 478 c. In the openings, the conductor476 a and the conductor 476 b are embedded.

The insulator 489 includes an opening overlapping with a channelformation region of the transistor 3300, an opening reaching theconductor 476 a, and an opening reaching the conductor 476 b. In theopenings, the conductor 474 a, the conductor 474 b, and the conductor474 c are embedded.

The conductor 474 a may serve as a bottom gate electrode of thetransistor 3300. Alternatively, for example, electrical characteristicssuch as the threshold voltage of the transistor 3300 may be controlledby application of a constant potential to the conductor 474 a. Furtheralternatively, for example, the conductor 474 a and the conductor 504that is a top gate electrode of the transistor 3300 may be electricallyconnected to each other. Thus, the on-state current of the transistor3300 can be increased. A punch-through phenomenon can be suppressed;thus, stable electrical characteristics in a saturation region of thetransistor 3300 can be obtained.

The insulator 490 includes an opening reaching the conductor 474 b andan opening reaching the conductor 474 c. Note that the insulator 490corresponds to the insulator 103 in the above embodiment and thus, thedescription of the insulator 103 can be referred to for details aboutthe insulator 490. As described in the above embodiment, the insulator490 is provided to cover the conductors 474 a to 474 c except for theopenings, whereby extraction of oxygen from the insulator 491 by theconductors 474 a to 474 c can be prevented. Accordingly, oxygen can beeffectively supplied from the insulator 491 to an oxide semiconductor ofthe transistor 3300.

The insulator 491 includes the opening reaching the conductor 474 b andthe opening reaching the conductor 474 c. Note that the insulator 491corresponds to the insulator 104 in the above embodiment and thus, thedescription of the insulator 104 can be referred to for details aboutthe insulator 491.

As described in the above embodiment, the amounts of water and hydrogenin the insulator 491 can be reduced, so that defect states can beprevented from being formed in the oxide semiconductor of the transistor2100. Accordingly, the electrical characteristics of the transistor 2100can be stabilized.

Such an insulator in which water and hydrogen are reduced may be used asan insulator other than the insulator 491, such as the insulator 466,the insulator 468, the insulator 489, or the insulator 493.

Although insulators that correspond to the insulators 105 and 101 in thetransistor are not illustrated in FIG. 24 , these insulators may beprovided. For example, an insulator that corresponds to the insulator101 may be provided between the insulator 468 and the insulator 489, andan insulator that corresponds to the insulator 105 may be providedbetween the insulator 489 and the insulator 490. In particular, theinsulator that has a function of blocking water, hydrogen, and the likeand corresponds to the insulator 101 may be provided between theinsulator 468 and the insulator 489 and the amounts of water andhydrogen in the insulator 491 are reduced in the above-described manner,whereby defect states can be further prevented from being formed in theoxide semiconductor of the transistor 3300.

The insulator 492 includes an opening reaching the conductor 474 bthrough the conductor 516 b that is one of a source electrode and adrain electrode of the transistor 3300, an opening reaching theconductor 514 that overlaps with the conductor 516 a that is the otherof the source electrode and the drain electrode of the transistor 3300,with the insulator 511 positioned therebetween, an opening reaching theconductor 504 that is a gate electrode of the transistor 3300, and anopening reaching the conductor 474 c through the conductor 516 a that isthe other of the source electrode and the drain electrode of thetransistor 3300. Note that the insulator 492 corresponds to theinsulator 116 in the above embodiment and thus, the description of theinsulator 116 can be referred to for details about the insulator 492.

The insulator 493 includes an opening reaching the conductor 474 bthrough the conductor 516 b that is one of a source electrode and adrain electrode of the transistor 3300, an opening reaching theconductor 514 that overlaps with the conductor 516 a that is the otherof the source electrode and the drain electrode of the transistor 3300,with the insulator 511 positioned therebetween, an opening reaching theconductor 504 that is a gate electrode of the transistor 3300, and anopening reaching the conductor 474 c through the conductor 516 a that isthe other of the source electrode and the drain electrode of thetransistor 3300. In the openings, the conductor 496 a, the conductor 496b, the conductor 496 c, and the conductor 496 d are embedded. Note thatin some cases, an opening provided in a component of the transistor 3300or the like is positioned between openings provided in other components.

The insulator 494 includes an opening reaching the conductor 496 a, anopening reaching the conductor 496 b, and an opening reaching theconductor 496 c. In the openings, the conductors 498 a, 498 b, and 498 care embedded.

At least one of the insulators 464, 466, 468, 489, 493, and 494preferably has a function of blocking oxygen and impurities such ashydrogen. When an insulator that has a function of blocking oxygen andimpurities such as hydrogen is placed near the transistor 3300, theelectrical characteristics of the transistor 3300 can be stable.

The source or drain of the transistor 3200 is electrically connected tothe conductor 516 b that is one of the source electrode and the drainelectrode of the transistor 3300 through the conductor 480 b, theconductor 478 b, the conductor 476 a, the conductor 474 b, and theconductor 496 c. The conductor 454 that is the gate electrode of thetransistor 3200 is electrically connected to the conductor 516 a that isthe other of the source electrode and the drain electrode of thetransistor 3300 through the conductor 480 c, the conductor 478 c, theconductor 476 b, the conductor 474 c, and the conductor 496 d.

The capacitor 3400 includes the conductor 516 a that is the other of thesource electrode and the drain electrode of the transistor 3300, theconductor 514, and the insulator 511. The insulator 511 is preferablyused in some cases because the insulator 511 can be formed in the samestep as the insulator functioning as a gate insulator of the transistor3300, leading to an increase in productivity. A layer formed in the samestep as the conductor 504 functioning as the gate electrode of thetransistor 3300 is preferably used as the conductor 514 in some cases,leading to an increase in productivity.

For the structures of other components, the description of FIG. 24 andthe like can be referred to as appropriate.

A semiconductor device in FIG. 29 is the same as the semiconductordevice in FIG. 28 except for the structure of the transistor 3200.Therefore, the description of the semiconductor device in FIG. 28 isreferred to for the semiconductor device in FIG. 29 . Specifically, inthe semiconductor device in FIG. 29 , the transistor 3200 is a Fin-typetransistor. For the Fin-type transistor 3200, the description of thetransistor 2200 in FIG. 25 is referred to. Note that although thetransistor 2200 is illustrated as a p-channel transistor in FIG. 25 ,the transistor 3200 may be an n-channel transistor.

A semiconductor device in FIG. 30 is the same as the semiconductordevice in FIG. 28 except for the structure of the transistor 3200.Therefore, the description of the semiconductor device in FIG. 28 isreferred to for the semiconductor device in FIG. 30 . Specifically, inthe semiconductor device in FIG. 30 , the transistor 3200 is provided inthe semiconductor substrate 450 that is an SOI substrate. For thetransistor 3200, which is provided in the semiconductor substrate 450(SOI substrate), the description of the transistor 2200 in FIG. 26 isreferred to. Note that although the transistor 2200 is illustrated as ap-channel transistor in FIG. 26 , the transistor 3200 may be ann-channel transistor.

<Memory Device 2>

The semiconductor device in FIG. 27B is different from the semiconductordevice in FIG. 27A in that the transistor 3200 is not provided. Also inthis case, data can be written and retained in a manner similar to thatof the semiconductor device in FIG. 27A.

Reading of data in the semiconductor device in FIG. 27B is described.When the transistor 3300 is brought into an on state, the third wiring3003 which is in a floating state and the capacitor 3400 are broughtinto conduction, and the electric charge is redistributed between thethird wiring 3003 and the capacitor 3400. As a result, the potential ofthe third wiring 3003 is changed. The amount of change in the potentialof the third wiring 3003 varies depending on the potential of the oneelectrode of the capacitor 3400 (or the electric charge accumulated inthe capacitor 3400).

For example, the potential of the third wiring 3003 after the chargeredistribution is (C_(B)×V_(B0)+C×V)/(C_(B)+C), where V is the potentialof the one electrode of the capacitor 3400, C is the capacitance of thecapacitor 3400, CB is the capacitance component of the third wiring3003, and V_(B0) is the potential of the third wiring 3003 before thecharge redistribution. Thus, it can be found that, assuming that thememory cell is in either of two states in which the potential of the oneelectrode of the capacitor 3400 is V₁ and V₀ (V₁>V₀), the potential ofthe third wiring 3003 in the case of retaining the potential V₁(=(C_(B)×V_(B0)+C×V₁)/(C_(B)+C)) is higher than the potential of thethird wiring 3003 in the case of retaining the potential V₀(=(C_(B)×V_(B0)+C×V₀)/(C_(B)+C)).

Then, by comparing the potential of the third wiring 3003 with apredetermined potential, data can be read.

In this case, a transistor including the first semiconductor may be usedfor a driver circuit for driving a memory cell, and a transistorincluding the second semiconductor may be stacked over the drivercircuit as the transistor 3300.

When including a transistor using an oxide semiconductor and having alow off-state current, the semiconductor device described above canretain stored data for a long time. In other words, power consumption ofthe semiconductor device can be reduced because refresh operationbecomes unnecessary or the frequency of refresh operation can beextremely low. Moreover, stored data can be retained for a long timeeven when power is not supplied (note that a potential is preferablyfixed).

In the semiconductor device, a high voltage is not needed for writingdata and deterioration of elements is less likely to occur. Unlike in aconventional nonvolatile memory, for example, it is not necessary toinject and extract electrons into and from a floating gate; thus, aproblem such as deterioration of an insulator is not caused. That is,the semiconductor device of one embodiment of the present invention doesnot have a limit on the number of times data can be rewritten, which isa problem of a conventional nonvolatile memory, and the reliabilitythereof is drastically improved. Furthermore, data is written dependingon the on/off state of the transistor, whereby high-speed operation canbe achieved.

<Memory Device 3>

A modification example of the semiconductor device (memory device)illustrated in FIG. 27A is described with reference to a circuit diagramin FIG. 31 .

The semiconductor device illustrated in FIG. 31 includes a transistor4100, a transistor 4200, a transistor 4300, a transistor 4400, acapacitor 4500, and a capacitor 4600. Here, a transistor similar to thetransistor 3200 can be used as the transistor 4100, and transistorssimilar to the transistor 3300 can be used as the transistors 4200,4300, and 4400. Although not illustrated in FIG. 31 , a plurality ofsemiconductor devices in FIG. 31 are provided in a matrix. Thesemiconductor devices in FIG. 31 can control writing and reading of adata voltage in accordance with a signal or a potential supplied to awiring 4001, a wiring 4003, a wiring 4005, a wiring 4006, a wiring 4007,a wiring 4008, and a wiring 4009.

One of a source and a drain of the transistor 4100 is connected to thewiring 4003. The other of the source and the drain of the transistor4100 is connected to the wiring 4001. Although the transistor 4100 is ap-channel transistor in FIG. 31 , the transistor 4100 may be ann-channel transistor.

The semiconductor device in FIG. 31 includes two data retentionportions. For example, a first data retention portion retains anelectric charge between one of a source and a drain of the transistor4400, one electrode of the capacitor 4600, and one of a source and adrain of the transistor 4200 which are connected to a node FG1. A seconddata retention portion retains an electric charge between a gate of thetransistor 4100, the other of the source and the drain of the transistor4200, one of a source and a drain of the transistor 4300, and oneelectrode of the capacitor 4500 which are connected to a node FG2.

The other of the source and the drain of the transistor 4300 isconnected to the wiring 4003. The other of the source and the drain ofthe transistor 4400 is connected to the wiring 4001. A gate of thetransistor 4400 is connected to the wiring 4005. A gate of thetransistor 4200 is connected to the wiring 4006. A gate of thetransistor 4300 is connected to the wiring 4007. The other electrode ofthe capacitor 4600 is connected to the wiring 4008. The other electrodeof the capacitor 4500 is connected to the wiring 4009.

The transistors 4200, 4300, and 4400 each function as a switch forcontrol of writing a data voltage and retaining an electric charge. Notethat, as each of the transistors 4200, 4300, and 4400, it is preferableto use a transistor having a low current that flows between a source anda drain in an off state (low off-state current). As an example of thetransistor with a low off-state current, a transistor including an oxidesemiconductor in its channel formation region (an OS transistor) ispreferably used. An OS transistor has a low off-state current and can beformed to overlap with a transistor including silicon, for example.Although the transistors 4200, 4300, and 4400 are n-channel transistorsin FIG. 31 , the transistors 4200, 4300, and 4400 may be p-channeltransistors.

The transistors 4200 and 4300 and the transistor 4400 are preferablyprovided in different layers even when the transistors 4200, 4300, and4400 are transistors including oxide semiconductors. In other words, thesemiconductor device in FIG. 31 preferably includes, as illustrated inFIG. 31 , a first layer 4021 where the transistor 4100 is provided, asecond layer 4022 where the transistors 4200 and 4300 are provided, anda third layer 4023 where the transistor 4400 is provided. By stackinglayers where transistors are provided, the circuit area can be reduced,so that the size of the semiconductor device can be reduced.

Next, operation of writing data to the semiconductor device illustratedin FIG. 31 is described.

First, operation of writing data voltage to the data retention portionconnected to the node FG1 (hereinafter referred to as writing operation1) is described. In the following description, data voltage written tothe data retention portion connected to the node FG1 is V_(D1), and thethreshold voltage of the transistor 4100 is V_(th).

In the writing operation 1, the potential of the wiring 4003 is set atV_(D1), and after the potential of the wiring 4001 is set at a groundpotential, the wiring 4001 is brought into an electrically floatingstate. The wirings 4005 and 4006 are set at a high level. The wirings4007 to 4009 are set at a low level. Then, the potential of the node FG2in the electrically floating state is increased, so that a current flowsthrough the transistor 4100. The current flows through the transistor4100, so that the potential of the wiring 4001 is increased. Thetransistors 4400 and 4200 are turned on. Thus, as the potential of thewiring 4001 is increased, the potentials of the nodes FG1 and FG2 areincreased. When the potential of the node FG2 is increased and a voltage(V_(gs)) between the gate and the source of the transistor 4100 becomesthe threshold voltage Vth of the transistor 4100, the current flowingthrough the transistor 4100 is decreased. Accordingly, the potentials ofthe wiring 4001 and the nodes FG1 and FG2 stop increasing, so that thepotentials of the nodes FG1 and FG2 are fixed at “V_(D1)-V_(th)” inwhich V_(D1) is decreased by V_(th).

When a current flows through the transistor 4100, V_(D1) supplied to thewiring 4003 is supplied to the wiring 4001, so that the potentials ofthe nodes FG1 and FG2 are increased. When the potential of the node FG2becomes “V_(D1)-V_(th)” with the increase in the potentials, V_(gs) ofthe transistor 4100 becomes Vth, so that the current flow is stopped.

Next, operation of writing data voltage to the data retention portionconnected to the node FG2 (hereinafter referred to as writing operation2) is described. In the following description, data voltage written tothe data retention portion connected to the node FG2 is V_(D2).

In the writing operation 2, the potential of the wiring 4001 is set atV_(D2), and after the potential of the wiring 4003 is set at a groundpotential, the wiring 4003 is brought into an electrically floatingstate. The wiring 4007 is set at the high level. The wirings 4005, 4006,4008, and 4009 are set at the low level. The transistor 4300 is turnedon, so that the wiring 4003 is set at the low level. Thus, the potentialof the node FG2 is decreased to the low level, so that the current flowsthrough the transistor 4100. By the current flow, the potential of thewiring 4003 is increased. The transistor 4300 is turned on. Thus, as thepotential of the wiring 4003 is increased, the potential of the node FG2is increased. When the potential of the node FG2 is increased and V_(gs)of the transistor 4100 becomes Vth of the transistor 4100, the currentflowing through the transistor 4100 is decreased. Accordingly, anincrease in the potentials of the wiring 4003 and the node FG2 isstopped, so that the potential of the node FG2 is fixed at“V_(D2)-V_(th)” in which V_(D2) is decreased by V_(th).

In other words, when a current flows through the transistor 4100, V_(D2)supplied to the wiring 4001 is supplied to the wiring 4003, so that thepotential of the node FG2 is increased. When the potential of the nodeFG2 becomes “V_(D2)-V_(th)” with the increase in the potential, V_(gs)of the transistor 4100 becomes Vth, so that the current flow is stopped.At this time, the transistors 4200 and 4400 are off and the potential ofthe node FG1 remains at “V_(D1)-V_(th)” written in the writing operation1.

In the semiconductor device in FIG. 31 , after data voltages are writtento the plurality of data retention portions, the wiring 4009 is set atthe high level, so that the potentials of the nodes FG1 and FG2 areincreased. Then, the transistors are turned off to stop movement ofelectric charges; thus, the written data voltages are retained.

By the above-described writing operation of the data voltage to thenodes FG1 and FG2, the data voltages can be retained in the plurality ofdata retention portions. Although examples where “V_(D1)-V_(th)” and“V_(D2)-V_(th)” are used as the written potentials are described, theyare data voltages corresponding to multilevel data. Therefore, in thecase where the data retention portions each retain 4-bit data, 16-value“V_(D1)-V_(th)” and 16-value “V_(D2)-V_(th)” can be obtained.

Next, operation of reading data from the semiconductor deviceillustrated in FIG. 31 is described.

First, operation of reading data voltage to the data retention portionconnected to the node FG2 (hereinafter referred to as reading operation1) is described.

In the reading operation 1, after precharge is performed, the wiring4003 in an electrically floating state is discharged. The wirings 4005to 4008 are set low. When the wiring 4009 is set low, the potential ofthe node FG2 which is electrically floating is set at “V_(D2)−V_(th).”The potential of the node FG2 is decreased, so that a current flowsthrough the transistor 4100. By the current flow, the potential of thewiring 4003 which is electrically floating is decreased. As thepotential of the wiring 4003 is decreased, V_(gs) of the transistor 4100is decreased. When V_(gs) of the transistor 4100 becomes Vth of thetransistor 4100, the current flowing through the transistor 4100 isdecreased. In other words, the potential of the wiring 4003 becomes“V_(D2)” which is larger than the potential of the node FG2,“V_(D2)-V_(th),” by Vth. The potential of the wiring 4003 corresponds tothe data voltage of the data retention portion connected to the nodeFG2. The data voltage of the read analog value is subjected to A/Dconversion, so that data of the data retention portion connected to thenode FG2 is obtained.

In other words, the wiring 4003 after precharge is brought into afloating state and the potential of the wiring 4009 is changed from highto low, whereby a current flows through the transistor 4100. When thecurrent flows, the potential of the wiring 4003 which is in a floatingstate is decreased to be “V_(D2).” In the transistor 4100, V_(gs)between “V_(D2)-V_(th)” of the node FG2 and “V_(D2)” of the wiring 4003becomes V_(th), so that the current stops. Then, “V_(D2)” written in thewriting operation 2 is read to the wiring 4003.

After data in the data retention portion connected to the node FG2 isobtained, the transistor 4300 is turned on to discharge “V_(D2)-V_(th)”of the node FG2.

Then, the electric charges retained in the node FG1 are distributedbetween the node FG1 and the node FG2, data voltage in the dataretention portion connected to the node FG1 is transferred to the dataretention portion connected to the node FG2. The wirings 4001 and 4003are set low. The wiring 4006 is set high. The wiring 4005 and thewirings 4007 to 4009 are set low. When the transistor 4200 is turned on,the electric charges in the node FG1 are distributed between the nodeFG1 and the node FG2.

Here, the potential after the electric charge distribution is decreasedfrom the written potential, “V_(D1)-V_(th).” Thus, the capacitance ofthe capacitor 4600 is preferably larger than the capacitance of thecapacitor 4500. Alternatively, the potential written to the node FG1,“V_(D1)-V_(th),” is preferably larger than the potential correspondingto the same data, “V_(D2)-V_(th).” By changing the ratio of thecapacitances and setting the written potential larger in advance asdescribed above, a decrease in potential after the electric chargedistribution can be suppressed. The change in potential due to theelectric charge distribution is described later.

Next, operation of reading data voltage to the data retention portionconnected to the node FG1 (hereinafter referred to as reading operation2) is described.

In the reading operation 2, the wiring 4003 which is brought into anelectrically floating state after precharge is discharged. The wirings4005 to 4008 are set low. The wiring 4009 is set high at the time ofprecharge and then, set low. When the wiring 4009 is set low, thepotential of the node FG2 which is electrically floating is set at“V_(D1)-V_(th).” The potential of the node FG2 is decreased, so that acurrent flows through the transistor 4100. The current flows, so thatthe potential of the wiring 4003 which is electrically floating isdecreased. As the potential of the wiring 4003 is decreased, V_(gs) ofthe transistor 4100 is decreased. When V_(gs) of the transistor 4100becomes Vth of the transistor 4100, the current flowing through thetransistor 4100 is decreased. In other words, the potential of thewiring 4003 becomes “V_(D1)” which is larger than the potential of thenode FG2, “V_(D1)-V_(th),” by V_(th). The potential of the wiring 4003corresponds to the data voltage of the data retention portion connectedto the node FG1. The data voltage of the read analog value is subjectedto A/D conversion, so that data of the data retention portion connectedto the node FG1 is obtained. The above is the reading operation of thedata voltage of the data retention portion connected to the node FG1.

In other words, the wiring 4003 after precharge is brought into afloating state and the potential of the wiring 4009 is changed from highto low, whereby a current flows through the transistor 4100. When thecurrent flows, the potential of the wiring 4003 which is in a floatingstate is decreased to be “V_(D1)” In the transistor 4100, V_(gs) between“V_(D1)-V_(th)” of the node FG2 and “V_(D1)” of the wiring 4003 becomesVth, so that the current stops. Then, “V_(D1)” written in the writingoperation 1 is read to the wiring 4003.

In the above-described reading operation of data voltages from the nodesFG1 and FG2, the data voltages can be read from the plurality of dataretention portions. For example, 4-bit (16-level) data is retained ineach of the node FG1 and the node FG2, whereby 8-bit (256-level) datacan be retained in total. Although the first to third layers 4021 to4023 are provided in the structure illustrated in FIG. 31 , the storagecapacity can be increased by adding layers without increasing the areaof the semiconductor device.

The read potential can be read as a voltage larger than the written datavoltage by V_(th). Therefore, V_(th) of “V_(D1)-V_(th)” and V_(th) of“V_(D2)-V_(th)” written in the writing operation can be canceled to beread. As a result, the storage capacity per memory cell can be improvedand read data can be close to accurate data; thus, the data reliabilitybecomes excellent.

FIG. 32 is a cross-sectional view of a semiconductor device thatcorresponds to FIG. 31 . The semiconductor device illustrated in FIG. 32includes the transistors 4100, 4200, 4300, and 4400 and the capacitors4500 and 4600. Here, the transistor 4100 is formed in the first layer4021, the transistors 4200 and 4300 and the capacitor 4500 are formed inthe second layer 4022, and the transistor 4400 and the capacitor 4600are formed in the third layer 4023.

Here, the description of the transistor 3300 can be referred to for thetransistors 4200, 4300, and 4400, and the description of the transistor3200 can be referred to for the transistor 4100. The description madewith reference to FIG. 28 can be appropriately referred to for otherwirings, other insulators, and the like.

Note that the capacitors 4500 and 4600 are formed by including theconductive layers each having a trench-like shape, while the conductivelayer of the capacitor 3400 in the semiconductor device in FIG. 28 isparallel to the substrate. With this structure, a larger capacity can beobtained without increasing the occupation area.

<Memory Device 4>

The semiconductor device in FIG. 27C is different from the semiconductordevice in FIG. 27A in that the transistor 3500 and a sixth wiring 3006are included. Also in this case, data can be written and retained in amanner similar to that of the semiconductor device in FIG. 27A. Atransistor similar to the transistor 3200 described above can be used asthe transistor 3500.

The sixth wiring 3006 is electrically connected to a gate of thetransistor 3500, one of a source and a drain of the transistor 3500 iselectrically connected to the drain of the transistor 3200, and theother of the source and the drain of the transistor 3500 is electricallyconnected to the third wiring 3003.

FIG. 33 illustrates an example of a cross-sectional view of thesemiconductor device illustrated in FIG. 27C. FIG. 34 illustrates anexample of a cross section in a B3-B4 direction that is substantiallyperpendicular to a B1-B2 direction in FIG. 33 . The semiconductor deviceillustrated in FIG. 27C, FIG. 33 , and FIG. 34 includes five layers 1627to 1631. The layer 1627 includes the transistor 3200, the transistor3500, and a transistor 3600. The layer 1628 and the layer 1629 includethe transistor 3300.

The layer 1627 includes a substrate 1400, the transistors 3200, 3500,and 3600 over the substrate 1400, an insulator 1464 over the transistor3200 and the like, and plugs such as a plug 1541. The plug 1541 or thelike is connected to, for example, a gate electrode, a source electrode,a drain electrode, or the like of the transistor 3200 or the like. Theplug 1541 is preferably formed to be embedded in the insulator 1464.

The description of the transistor 2200 can be referred to for thetransistors 3200, 3500, and 3600.

The insulator 1464 can be formed using, for example, silicon oxide,silicon oxynitride, silicon nitride oxide, silicon nitride, aluminumoxide, aluminum oxynitride, aluminum nitride oxide, aluminum nitride, orthe like.

The insulator 1464 can be formed by a sputtering method, a CVD method(including a thermal CVD method, an MOCVD method, a PECVD method, andthe like), an MBE method, an ALD method, a PLD method, or the like. Inparticular, it is preferable that the insulator be formed by a CVDmethod, further preferably a plasma CVD method because coverage can befurther improved. It is preferable to use a thermal CVD method, an MOCVDmethod, or an ALD method in order to reduce plasma damage.

Alternatively, the insulator 1464 can be formed using siliconcarbonitride, silicon oxycarbide, or the like. Further alternatively,undoped silicate glass (USG), boron phosphorus silicate glass (BPSG),borosilicate glass (BSG), or the like can be used. USG, BPSG, and thelike may be formed by an atmospheric pressure CVD method. Alternatively,hydrogen silsesquioxane (HSQ) or the like may be applied by a coatingmethod.

The insulator 1464 may have a single-layer structure or a stacked-layerstructure of a plurality of materials.

In FIG. 33 , the insulator 1464 is formed of two layers, i.e., aninsulator 1464 a and an insulator 1464 b over the insulator 1464 a.

The insulator 1464 a is preferably formed over a region 1476 of thetransistor 3200, a conductor 1454 functioning as a gate of thetransistor 3200 and the like, and the like with high adhesion or highcoverage.

As an example of the insulator 1464 a, silicon nitride formed by a CVDmethod can be used. Here, the insulator 1464 a preferably containshydrogen in some cases. When the insulator 1464 a contains hydrogen, adefect or the like in the substrate 1400 is reduced and thecharacteristics of the transistor 3200 and the like are improved in somecases. For example, in the case where the substrate 1400 is formed usinga material containing silicon, a defect such as a dangling bond in thesilicon can be terminated by hydrogen.

The parasitic capacitance formed between a conductor under the insulator1464 a, such as the conductor 1454, and a conductor over the insulator1464 b, such as a conductor 1511, is preferably small. Thus, theinsulator 1464 b preferably has a low dielectric constant. Thedielectric constant of the insulator 1464 b is preferably lower thanthat of an insulator 1462 that functions as a gate insulator of thetransistor 3200 and the like. The dielectric constant of the insulator1464 b is preferably lower than that of the insulator 1464 a. Forexample, the relative dielectric constant of the insulator 1464 b ispreferably lower than 4, more preferably lower than 3. For example, therelative dielectric constant of the insulator 1464 b is preferably 0.7times or less that of the insulator 1464 a, more preferably 0.6 times orless that of the insulator 1464 a.

Here, for example, silicon nitride and USG can be used as the insulator1464 a and the insulator 1464 b, respectively.

When the insulator 1464 a, an insulator 1581 a, and the like are formedusing a material with low copper permeability, such as silicon nitrideor silicon carbonitride, the diffusion of copper into a layer under theinsulator 1464 a or the like and a layer over the insulator 1581 a orthe like can be suppressed when copper is included in the conductor 1511or the like.

An impurity such as copper released from a top surface of the conductor1511 b not covered with the conductor 1511 a might be diffused into alayer over the conductor 1511 b through an insulator 1584 or the like,for example. Thus, the insulator 1584 over the conductor 1511 b ispreferably formed using a material through which an impurity such ascopper is hardly allowed to pass. For example, the insulator 1584 mayhave a stacked structure of the insulator 1581 a and an insulator 1581b.

The layer 1628 includes an insulator 1581, the insulator 1584 over theinsulator 1581, an insulator 1571 over the insulator 1584, an insulator1585 over the insulator 1571, the conductor 1511 and the like over theinsulator 1464, a plug 1543 and the like connected to the conductor 1511and the like, and a conductor 1513 over the insulator 1571. Theconductor 1511 is preferably formed to be embedded in the insulator1581. The plug 1543 and the like are preferably formed to be embedded inthe insulator 1584 and the insulator 1571. The conductor 1513 ispreferably formed to be embedded in the insulator 1585.

The layer 1628 may include a conductor 1413. The conductor 1413 ispreferably formed to be embedded in the insulator 1585.

The insulator 1584 and the insulator 1585 can be formed using, forexample, silicon oxide, silicon oxynitride, silicon nitride oxide,silicon nitride, aluminum oxide, aluminum oxynitride, aluminum nitrideoxide, aluminum nitride, or the like.

The insulator 1584 and the insulator 1585 can be formed by a sputteringmethod, a CVD method (including a thermal CVD method, an MOCVD method, aPECVD method, and the like), an MBE method, an ALD method, a PLD method,or the like. In particular, it is preferable that the insulator beformed by a CVD method, further preferably a plasma CVD method becausecoverage can be further improved. Furthermore, it is preferable to usetetraethoxysilane (TEOS) (chemical formula: Si(OC₂H₅)₄) as a depositiongas, and it is more preferable to perform the deposition while heatingis performed. The insulators 1584 and 1585 and the like are formed inthis manner, whereby the hydrogen concentration in the film can bereduced. Note that in the case where heating is performed, thepreferable temperature is within a relatively low temperature range (forexample, higher than or equal to 350° C. and lower than or equal to 445°C.). Such an insulator film whose hydrogen concentration is reduced maybe used as another interlayer insulating film.

Note that it is preferable to use a thermal CVD method, an MOCVD method,or an ALD method in order to reduce plasma damage.

Alternatively, the insulator 1584 and the insulator 1585 can be formedusing silicon carbide, silicon carbonitride, silicon oxycarbide, or thelike. Further alternatively, undoped silicate glass (USG), boronphosphorus silicate glass (BPSG), borosilicate glass (BSG), or the likecan be used. USG, BPSG, and the like may be formed by an atmosphericpressure CVD method. Alternatively, hydrogen silsesquioxane (HSQ) or thelike may be applied by a coating method.

Each of the insulators 1584 and 1585 may have a single-layer structureor a stacked-layer structure of a plurality of materials.

The insulator 1581 may have a stacked-layer structure of a plurality oflayers. For example, the insulator 1581 has a two-layer structure of theinsulator 1581 a and the insulator 1581 b over the insulator 1581 a asshown in FIG. 33 .

The plug 1543 has a portion projecting above the insulator 1571.

A conductive material such as a metal material, an alloy material, or ametal oxide material can be used as a material of the conductor 1511,the conductor 1513, the conductor 1413, the plug 1543, and the like. Forexample, a single-layer structure or a stacked-layer structure using anyof metals such as aluminum, titanium, chromium, nickel, copper, yttrium,zirconium, niobium, molybdenum, silver, tantalum, and tungsten, or analloy containing any of these metals as a main component can be used.Alternatively, a metal nitride such as tungsten nitride, molybdenumnitride, or titanium nitride can be used.

The conductors such as the conductor 1511 and the conductor 1513preferably function as wirings in the semiconductor device illustratedin FIG. 27C. Therefore, these conductors are also referred to as wiringsor wiring layers in some cases. These conductors are preferablyconnected to each other via plugs such as the plug 1543.

For the insulator 1581, the description of the insulator 1464 isreferred to. The insulator 1581 may have a single-layer structure or astacked-layer structure of a plurality of materials. In the exampleshown in FIG. 33 , the insulator 1581 has a two-layer structure of theinsulator 1581 a and the insulator 1581 b over the insulator 1581 a. Fora material and a formation method that can be used for the insulator1581 a and the insulator 1581 b, the description of the material and theformation method that can be used for the insulator 1464 a and theinsulator 1464 b can be referred to.

As an example of the insulator 1581 a, silicon nitride formed by a CVDmethod can be used. In a semiconductor element included in thesemiconductor device illustrated in FIG. 27C, such as the transistor3300, hydrogen is diffused into the semiconductor element, so that thecharacteristics of the semiconductor element are degraded in some cases.In view of this, a film that releases a small amount of hydrogen ispreferably used as the insulator 1581 a. The released amount of hydrogencan be measured by thermal desorption spectroscopy (TDS), for example.In TDS analysis, the amount of hydrogen released from the insulator 1581a which is converted into hydrogen atoms is, for example, less than orequal to 5×10²⁰ atoms/cm³, preferably less than or equal to 2×10²⁰atoms/cm³, more preferably less than or equal to 1×10²⁰ atoms/cm³ in therange of 50° C. to 500° C. The amount of hydrogen released from theinsulator 1581 a per area of the insulating film, which is convertedinto hydrogen atoms, is less than or equal to 5×10¹⁵ atoms/cm²,preferably less than or equal to 2×10¹⁵ atoms/cm², more preferably lessthan or equal to 1×10¹⁵ atoms/cm², for example.

Silicon nitride from which a small number of hydrogen atoms are releasedmay be used for not only the insulator 1581 a but also an insulator in alayer over the insulator 1581 a illustrated in FIG. 33 . Instead of thesilicon nitride, an insulator similar to the insulator 104 described inthe above embodiment in which hydrogen and water are reduced may beused.

The dielectric constant of the insulator 1581 b is preferably lower thanthat of the insulator 1581 a. For example, the relative dielectricconstant of the insulator 1581 b is preferably lower than 4, morepreferably lower than 3. For example, the relative dielectric constantof the insulator 1581 b is preferably 0.7 times or less that of theinsulator 1581 a, more preferably 0.6 times or less that of theinsulator 1581 a.

The insulator 1571 is preferably formed using an insulating materialthrough which an impurity hardly passes. Preferably, the insulator 1571has low oxygen permeability, for example. Preferably, the insulator 1571has low hydrogen permeability, for example. Preferably, the insulator1571 has low water permeability, for example.

The insulator 1571 can be formed using a single-layer structure or astacked-layer structure using, for example, aluminum oxide, hafniumoxide, tantalum oxide, zirconium oxide, lead zirconate titanate (PZT),strontium titanate (SrTiO₃), (Ba,Sr)TiO₃ (BST), silicon nitride, or thelike. Alternatively, aluminum oxide, bismuth oxide, germanium oxide,niobium oxide, silicon oxide, titanium oxide, tungsten oxide, yttriumoxide, zirconium oxide, or gallium oxide may be added to the insulator,for example. Alternatively, the insulator may be subjected to nitridingtreatment to be oxynitride. A layer of silicon oxide, siliconoxynitride, or silicon nitride may be stacked over the insulator.Aluminum oxide is particularly preferable because of its excellentbarrier property against water and hydrogen.

The insulator 1571 is formed using, for example, silicon carbide,silicon carbonitride, or silicon oxycarbide.

The insulator 1571 may be a stack including a layer of a materialthrough which water and hydrogen are hardly allowed to pass and a layercontaining an insulating material. The insulator 1571 may be, forexample, a stack of a layer containing silicon oxide or siliconoxynitride, a layer containing a metal oxide, and the like.

The insulator 1571 included in the semiconductor device illustrated inFIG. 27C can suppress the diffusion of an element included in theconductor 1513, the conductor 1413, and the like into the insulator 1571and layers under the insulator 1571 (e.g., the insulator 1584, theinsulator 1581, and the layer 1627), for example.

In the case where the dielectric constant of the insulator 1571 ishigher than that of the insulator 1584, the thickness of the insulator1571 is preferably smaller than that of the insulator 1584. Here, therelative dielectric constant of the insulator 1584 is 0.7 times or lessthat of the insulator 1571, more preferably 0.6 times or less that ofthe insulator 1571, for example. The thickness of the insulator 1571 ispreferably greater than or equal to 5 nm and less than or equal to 200nm, more preferably greater than or equal to 5 nm and less than or equalto 60 nm, and the thickness of the insulator 1584 is preferably greaterthan or equal to 30 nm and less than or equal to 800 nm, more preferablygreater than or equal to 50 nm and less than or equal to 500 nm, forexample. The thickness of the insulator 1571 is preferably less than orequal to one-third of the thickness of the insulator 1584, for example.

The layer 1629 includes the transistor 3300 and plugs such as a plug1544 and a plug 1544 b. The plugs such as the plug 1544 and the plug1544 b are connected to the conductor 1513 in the layer 1628 and a gateelectrode, a source electrode, and a drain electrode of the transistor3300. The description of the transistor 20, the transistor 2100, and thelike can be referred to for the structure of the transistor 3300.

The transistor 3300 includes the conductor 1413, an insulator 1571 a, aninsulator 1402, a conductor 1416 a, a conductor 1416 b, a conductor1404, an insulator 1408, and an insulator 1591. For the conductor 1413,the insulator 1571 a, the insulator 1402, the conductor 1416 a, theconductor 1416 b, the conductor 1404, the insulator 1408, and theinsulator 1591, the description of the conductor 102, the insulator 103,the insulator 104, the conductor 108 a, the conductor 108 b, theconductor 114, the insulator 116, and the insulator 118, respectively,can be referred to.

An insulator 1402 a that corresponds to the insulator 105 in thetransistor 20 may be provided as illustrated in FIG. 76 and FIG. 77 .Note that FIG. 76 and FIG. 77 correspond to FIG. 33 and FIG. 34 , anddiffer from FIG. 33 and FIG. 34 only in that the insulator 1402 a isprovided. For example, the insulator 1402 a may be provided between theinsulator 1585 and the insulator 1571 a. Of the insulators 1402 a, 1571a, and 1402, the insulator 1571 a preferably includes an electron trapregion. When the insulators 1402 a and 1402 have a function ofinhibiting release of electrons, the electrons trapped in the insulator1571 a behave as if they are negative fixed charges. Therefore, thethreshold voltage of the transistor 3300 can be changed by injection ofelectrons into the insulator 1571 a. The injection of electrons into theinsulator 1571 a can be performed by applying a positive or negativepotential to the conductor 1413.

Since the amount of electron injection can be controlled by the timeduring which potential is applied to the conductor 1413 and/or the valueof applied potential, a desirable threshold voltage of the transistorcan be obtained. The potential applied to the conductor 1413 is set suchthat a tunneling current flows through the insulator 1402 a. Forexample, the applied potential is higher than or equal to 20 V and lowerthan or equal to 60 V, preferably higher than or equal to 24 V and lowerthan or equal to 50 V, more preferably higher than or equal to 30 V andlower than or equal to 45 V. The time during which potential is appliedis, for example, longer than or equal to 0.1 seconds and shorter than orequal to 20 seconds, preferably longer than or equal to 0.2 seconds andshorter than or equal to 10 seconds.

As in the above embodiment, the amounts of water and hydrogen containedin the insulator in a stacked film of insulators (in this embodiment, astacked film of the insulator 1585, the insulator 1402 a, the insulator1571 a, and the insulator 1402) provided between the insulator 1571 andthe insulator corresponding to the insulator 106 a of the transistor arepreferably small. When the insulator 1571 has a function of blockingwater and hydrogen as described above, water and hydrogen supplied to anoxide to be the insulator 106 a and the semiconductor 106 b of thetransistor 20 while the oxide is being deposited are those contained inthe insulator 1585, the insulator 1402 a, the insulator 1571 a, and theinsulator 1402. Accordingly, when the amounts of water and hydrogencontained in the stacked film of the insulator 1585, the insulator 1402a, the insulator 1571 a, and the insulator 1402 (in particular, theamounts of water and hydrogen contained in the insulator 1402) aresufficiently small at the time of deposition for the oxide, the amountsof water and hydrogen supplied to the oxide can be small.

The conductor 1416 a and the conductor 1416 b preferably include amaterial through which an element included in the plug 1544 b formed incontact with the top surfaces of the conductor 1416 a and the conductor1416 b is unlikely to pass.

Each of the conductor 1416 a and the conductor 1416 b may be formed ofstacked films. For example, each of the conductor 1416 a and theconductor 1416 b is formed of stacked layers of a first layer and asecond layer. Here, the first layer is formed over the oxidesemiconductor layer, and the second layer is formed over the firstlayer. For example, tungsten and tantalum nitride are used as the firstlayer and the second layer, respectively. Here, copper is used as theplug 1544 b or the like, for example. Copper is preferably used as aconductor such as a plug or a wiring because of its low resistance. Onthe other hand, copper is easily diffused; the diffusion of copper intoa semiconductor layer, a gate insulating film, or the like of atransistor degrades the transistor characteristics in some cases. Whentantalum nitride is included in the conductor 1416 a and the conductor1416 b, the diffusion of copper included in the plug 1544 b or the likeinto the oxide semiconductor layer can be suppressed in some cases.

The semiconductor device illustrated in FIG. 27C of one embodiment ofthe present invention preferably has a structure in which, in the casewhere an element and a compound that cause degradation ofcharacteristics of a semiconductor element are included in the plug, thewiring, or the like, the diffusion of the element and the compound intothe semiconductor element is suppressed.

The layer 1630 includes an insulator 1592, conductors such as aconductor 1514, and plugs such as a plug 1545. The plug 1545 and thelike are connected to the conductors such as the conductor 1514.

The layer 1631 includes a capacitor 3400. The capacitor 3400 includes aconductor 1516, a conductor 1517, and an insulator 1572. The insulator1572 includes a region positioned between the conductor 1516 and theconductor 1517. The layer 1631 preferably includes an insulator 1594 anda plug 1547 over the conductor 1517. The plug 1547 is preferably formedto be embedded in the insulator 1594. The layer 1631 preferably includesa conductor 1516 b connected to the plug included in the layer 1630 anda plug 1547 b over the conductor 1516 b.

The layer 1631 may include a wiring layer connected to the plug 1547 andthe plug 1547 b. In the example shown in FIG. 33 , the wiring layerincludes a conductor 1518 and the like connected to the plug 1547 andthe plug 1547 b, a plug 1548 over the conductor 1518, an insulator 1595,a conductor 1519 over the plug 1548, and an insulator 1599 over theconductor 1519. The plug 1548 is preferably formed to be embedded in theinsulator 1595. The insulator 1599 includes an opening over theconductor 1519.

The structure described in this embodiment can be used in appropriatecombination with any of the other structures described in the otherembodiments.

Embodiment 5

In this embodiment, an example of an imaging device including thetransistor or the like of one embodiment of the present invention isdescribed.

<Imaging Device>

An imaging device of one embodiment of the present invention isdescribed below.

FIG. 35A is a plan view illustrating an example of an imaging device 200of one embodiment of the present invention. The imaging device 200includes a pixel portion 210 and peripheral circuits for driving thepixel portion 210 (a peripheral circuit 260, a peripheral circuit 270, aperipheral circuit 280, and a peripheral circuit 290). The pixel portion210 includes a plurality of pixels 211 arranged in a matrix with p rowsand q columns (p and q are each an integer of 2 or more). The peripheralcircuit 260, the peripheral circuit 270, the peripheral circuit 280, andthe peripheral circuit 290 are each connected to the plurality of pixels211, and a signal for driving the plurality of pixels 211 is supplied.In this specification and the like, in some cases, a “peripheralcircuit” or a “driver circuit” indicate all of the peripheral circuits260, 270, 280, and 290. For example, the peripheral circuit 260 can beregarded as part of the peripheral circuit.

The imaging device 200 preferably includes a light source 291. The lightsource 291 can emit detection light P 1.

The peripheral circuit includes at least one of a logic circuit, aswitch, a buffer, an amplifier circuit, and a converter circuit. Theperipheral circuit may be formed over a substrate where the pixelportion 210 is formed. A semiconductor device such as an IC chip may beused as part or the whole of the peripheral circuit. Note that as theperipheral circuit, one or more of the peripheral circuits 260, 270,280, and 290 may be omitted.

As illustrated in FIG. 35B, the pixels 211 may be provided to beinclined in the pixel portion 210 included in the imaging device 200.When the pixels 211 are obliquely arranged, the distance between pixels(pitch) can be shortened in the row direction and the column direction.Accordingly, the quality of an image taken with the imaging device 200can be improved.

<Configuration Example 1 of Pixel>

The pixel 211 included in the imaging device 200 is formed with aplurality of subpixels 212, and each subpixel 212 is combined with afilter (color filter) which transmits light in a specific wavelengthrange, whereby data for achieving color image display can be obtained.

FIG. 36A is a top view showing an example of the pixel 211 with which acolor image is obtained. The pixel 211 illustrated in FIG. 36A includesa subpixel 212 provided with a color filter that transmits light in ared (R) wavelength range (also referred to as a subpixel 212R), asubpixel 212 provided with a color filter that transmits light in agreen (G) wavelength range (also referred to as a subpixel 212G), and asubpixel 212 provided with a color filter that transmits light in a blue(B) wavelength range (also referred to as a subpixel 212B). The subpixel212 can function as a photosensor.

The subpixel 212 (the subpixel 212R, the subpixel 212G, and the subpixel212B) is electrically connected to a wiring 231, a wiring 247, a wiring248, a wiring 249, and a wiring 250. In addition, the subpixel 212R, thesubpixel 212G, and the subpixel 212B are connected to respective wirings253 which are independently provided. In this specification and thelike, for example, the wiring 248 and the wiring 249 that are connectedto the pixel 211 in the n-th row are referred to as a wiring 248[n] anda wiring 249[n]. For example, the wiring 253 connected to the pixel 211in the m-th column is referred to as a wiring 253[m]. Note that in FIG.36A, the wirings 253 connected to the subpixel 212R, the subpixel 212G,and the subpixel 212B in the pixel 211 in the m-th column are referredto as a wiring 253[m]R, a wiring 253[m]G, and a wiring 253[m]B. Thesubpixels 212 are electrically connected to the peripheral circuitthrough the above wirings.

The imaging device 200 has a structure in which the subpixel 212 iselectrically connected to the subpixel 212 in an adjacent pixel 211which is provided with a color filter transmitting light in the samewavelength range as the subpixel 212, via a switch. FIG. 36B shows aconnection example of the subpixels 212: the subpixel 212 in the pixel211 arranged in the n-th (n is an integer greater than or equal to 1 andless than or equal to p) row and the m-th (m is an integer greater thanor equal to 1 and less than or equal to q) column and the subpixel 212in the adjacent pixel 211 arranged in an (n+1)-th row and the m-thcolumn. In FIG. 36B, the subpixel 212R arranged in the n-th row and them-th column and the subpixel 212R arranged in the (n+1)-th row and them-th column are connected to each other via a switch 201. The subpixel212G arranged in the n-th row and the m-th column and the subpixel 212Garranged in the (n+1)-th row and the m-th column are connected to eachother via a switch 202. The subpixel 212B arranged in the n-th row andthe m-th column and the subpixel 212B arranged in the (n+1)-th row andthe m-th column are connected to each other via a switch 203.

The color filter used in the subpixel 212 is not limited to red (R),green (G), and blue (B) color filters, and color filters that transmitlight of cyan (C), yellow (Y), and magenta (M) may be used. By provisionof the subpixels 212 that sense light in three different wavelengthranges in one pixel 211, a full-color image can be obtained.

The pixel 211 including the subpixel 212 provided with a color filtertransmitting yellow (Y) light may be provided, in addition to thesubpixels 212 provided with the color filters transmitting red (R),green (G), and blue (B) light. The pixel 211 including the subpixel 212provided with a color filter transmitting blue (B) light may beprovided, in addition to the subpixels 212 provided with the colorfilters transmitting cyan (C), yellow (Y), and magenta (M) light. Whenthe subpixels 212 sensing light in four different wavelength ranges areprovided in one pixel 211, the reproducibility of colors of an obtainedimage can be increased.

For example, in FIG. 36A, in regard to the subpixel 212 sensing light ina red wavelength range, the subpixel 212 sensing light in a greenwavelength range, and the subpixel 212 sensing light in a bluewavelength range, the pixel number ratio (or the light receiving arearatio) thereof is not necessarily 1:1:1. For example, the Bayerarrangement in which the pixel number ratio (the light receiving arearatio) is set at red:green:blue=1:2:1 may be employed. Alternatively,the pixel number ratio (the light receiving area ratio) of red and greento blue may be 1:6:1.

Although the number of subpixels 212 provided in the pixel 211 may beone, two or more subpixels are preferably provided. For example, whentwo or more subpixels 212 sensing light in the same wavelength range areprovided, the redundancy is increased, and the reliability of theimaging device 200 can be increased.

When an infrared (IR) filter that transmits infrared light and absorbsor reflects visible light is used as the filter, the imaging device 200that senses infrared light can be achieved.

Furthermore, when a neutral density (ND) filter (dark filter) is used,output saturation which occurs when a large amount of light enters aphotoelectric conversion element (light-receiving element) can beprevented. With a combination of ND filters with different dimmingcapabilities, the dynamic range of the imaging device can be increased.

Besides the above-described filter, the pixel 211 may be provided with alens. An arrangement example of the pixel 211, a filter 254, and a lens255 is described with cross-sectional views in FIGS. 37A and 37B. Withthe lens 255, the photoelectric conversion element can receive incidentlight efficiently. Specifically, as illustrated in FIG. 37A, light 256enters a photoelectric conversion element 220 through the lens 255, thefilter 254 (a filter 254R, a filter 254G, and a filter 254B), a pixelcircuit 230, and the like which are provided in the pixel 211.

As indicated by a region surrounded with dashed lines, however, part ofthe light 256 indicated by arrows might be blocked by some wirings 257.Thus, a preferable structure is such that the lens 255 and the filter254 are provided on the photoelectric conversion element 220 side asillustrated in FIG. 37B, whereby the photoelectric conversion element220 can efficiently receive the light 256. When the light 256 enters thephotoelectric conversion element 220 from the photoelectric conversionelement 220 side, the imaging device 200 with high sensitivity can beprovided.

As the photoelectric conversion element 220 illustrated in FIGS. 37A and37B, a photoelectric conversion element in which a p-n junction or ap-i-n junction is formed may be used.

The photoelectric conversion element 220 may be formed using a substancethat has a function of absorbing a radiation and generating electriccharges. Examples of the substance that has a function of absorbing aradiation and generating electric charges include selenium, lead iodide,mercury iodide, gallium arsenide, cadmium telluride, and cadmium zincalloy.

For example, when selenium is used for the photoelectric conversionelement 220, the photoelectric conversion element 220 can have a lightabsorption coefficient in a wide wavelength range, such as visiblelight, ultraviolet light, infrared light, X-rays, and gamma rays.

One pixel 211 included in the imaging device 200 may include thesubpixel 212 with a first filter in addition to the subpixel 212illustrated in FIGS. 36A and 36B.

<Configuration Example 2 of Pixel>

An example of a pixel including a transistor using silicon and atransistor using an oxide semiconductor is described below.

FIGS. 38A and 38B are each a cross-sectional view of an element includedin an imaging device. The imaging device illustrated in FIG. 38Aincludes a transistor 351 including silicon over a silicon substrate300, transistors 352 and 353 which include an oxide semiconductor andare stacked over the transistor 351, and a photodiode 360 provided in asilicon substrate 300. The transistors and the photodiode 360 areelectrically connected to various plugs 370 and wirings 371. Inaddition, an anode 361 of the photodiode 360 is electrically connectedto the plug 370 through a low-resistance region 363.

The imaging device includes a layer 310 including the transistor 351provided on the silicon substrate 300 and the photodiode 360 provided inthe silicon substrate 300, a layer 320 which is in contact with thelayer 310 and includes the wirings 371, a layer 330 which is in contactwith the layer 320 and includes the transistors 352 and 353, and a layer340 which is in contact with the layer 330 and includes a wiring 372 anda wiring 373.

In the example of cross-sectional view in FIG. 38A, a light-receivingsurface of the photodiode 360 is provided on the side opposite to asurface of the silicon substrate 300 where the transistor 351 is formed.With this structure, a light path can be secured without an influence ofthe transistors and the wirings. Thus, a pixel with a high apertureratio can be formed. Note that the light-receiving surface of thephotodiode 360 can be the same as the surface where the transistor 351is formed.

In the case where a pixel is formed with use of only transistors usingan oxide semiconductor, the layer 310 may include the transistor usingan oxide semiconductor. Alternatively, the layer 310 may be omitted, andthe pixel may include only transistors using an oxide semiconductor.

In the case where a pixel is formed with use of only transistors usingsilicon, the layer 330 may be omitted. An example of a cross-sectionalview in which the layer 330 is not provided is shown in FIG. 38B.

Note that the silicon substrate 300 may be an SOI substrate.Furthermore, the silicon substrate 300 can be replaced with a substratemade of germanium, silicon germanium, silicon carbide, gallium arsenide,aluminum gallium arsenide, indium phosphide, gallium nitride, or anorganic semiconductor.

Here, an insulator 380 is provided between the layer 310 including thetransistor 351 and the photodiode 360 and the layer 330 including thetransistors 352 and 353. However, there is no limitation on the positionof the insulator 380.

Hydrogen in an insulator provided in the vicinity of a channel formationregion of the transistor 351 terminates dangling bonds of silicon;accordingly, the reliability of the transistor 351 can be improved. Incontrast, hydrogen in the insulator provided in the vicinity of thetransistor 352, the transistor 353, and the like becomes one of factorsgenerating a carrier in the oxide semiconductor. Thus, the hydrogen maycause a reduction of the reliability of the transistor 352, thetransistor 353, and the like. Therefore, in the case where thetransistor using an oxide semiconductor is provided over the transistorusing a silicon-based semiconductor, it is preferable that the insulator380 having a function of blocking hydrogen be provided between thetransistors. When the hydrogen is confined below the insulator 380, thereliability of the transistor 351 can be improved. In addition, thehydrogen can be prevented from being diffused from a part below theinsulator 380 to a part above the insulator 380; thus, the reliabilityof the transistor 352, the transistor 353, and the like can beincreased.

As the insulator 380, an insulator having a function of blocking oxygenor hydrogen is used, for example.

In the cross-sectional view in FIG. 38A, the photodiode 360 in the layer310 and the transistor in the layer 330 can be formed so as to overlapwith each other. Thus, the degree of integration of pixels can beincreased. In other words, the resolution of the imaging device can beincreased.

As illustrated in FIG. 39A1 and FIG. 39B1, part or the whole of theimaging device can be bent. FIG. 39A1 illustrates a state in which theimaging device is bent in the direction of a dashed-dotted line X1-X2.FIG. 39A2 is a cross-sectional view illustrating a portion indicated bythe dashed-dotted line X1-X2 in FIG. 39A1. FIG. 39A3 is across-sectional view illustrating a portion indicated by a dashed-dottedline Y1-Y2 in FIG. 39A1.

FIG. 39B1 illustrates a state where the imaging device is bent in thedirection of a dashed-dotted line X3-X4 and the direction of adashed-dotted line Y3-Y4. FIG. 39B2 is a cross-sectional viewillustrating a portion indicated by the dashed-dotted line X3-X4 in FIG.39B1. FIG. 39B3 is a cross-sectional view illustrating a portionindicated by the dashed-dotted line Y3-Y4 in FIG. 39B1.

The bent imaging device enables the curvature of field and astigmatismto be reduced. Thus, the optical design of lens and the like, which isused in combination of the imaging device, can be facilitated. Forexample, the number of lenses used for aberration correction can bereduced; accordingly, a reduction of size or weight of electronicdevices using the imaging device, and the like, can be achieved. Inaddition, the quality of a captured image can be improved.

The structures described in this embodiment can be used in appropriatecombination with any of the structures described in the otherembodiments.

Embodiment 6

In this embodiment, examples of CPUs including semiconductor devicessuch as the transistor of one embodiment of the present invention andthe above-described memory device are described.

<Configuration of CPU>

FIG. 40 is a block diagram illustrating a configuration example of a CPUincluding any of the above-described transistors as a component.

The CPU illustrated in FIG. 40 includes, over a substrate 1190, anarithmetic logic unit (ALU) 1191, an ALU controller 1192, an instructiondecoder 1193, an interrupt controller 1194, a timing controller 1195, aregister 1196, a register controller 1197, a bus interface 1198, arewritable ROM 1199, and a ROM interface 1189. A semiconductorsubstrate, an SOI substrate, a glass substrate, or the like is used asthe substrate 1190. The ROM 1199 and the ROM interface 1189 may beprovided over a separate chip. Needless to say, the CPU in FIG. 40 isjust an example in which the configuration has been simplified, and anactual CPU may have a variety of configurations depending on theapplication. For example, the CPU may have the following configuration:a structure including the CPU illustrated in FIG. 40 or an arithmeticcircuit is considered as one core; a plurality of such cores areincluded; and the cores operate in parallel. The number of bits that theCPU can process in an internal arithmetic circuit or in a data bus canbe 8, 16, 32, or 64, for example.

An instruction that is input to the CPU through the bus interface 1198is input to the instruction decoder 1193 and decoded therein, and then,input to the ALU controller 1192, the interrupt controller 1194, theregister controller 1197, and the timing controller 1195.

The ALU controller 1192, the interrupt controller 1194, the registercontroller 1197, and the timing controller 1195 conduct various controlsin accordance with the decoded instruction. Specifically, the ALUcontroller 1192 generates signals for controlling the operation of theALU 1191. While the CPU is executing a program, the interrupt controller1194 judges an interrupt request from an external input/output device ora peripheral circuit on the basis of its priority or a mask state, andprocesses the request. The register controller 1197 generates an addressof the register 1196, and reads/writes data from/to the register 1196 inaccordance with the state of the CPU.

The timing controller 1195 generates signals for controlling operationtimings of the ALU 1191, the ALU controller 1192, the instructiondecoder 1193, the interrupt controller 1194, and the register controller1197. For example, the timing controller 1195 includes an internal clockgenerator for generating an internal clock signal CLK2 based on areference clock signal CLK1, and supplies the internal clock signal CLK2to the above circuits.

In the CPU illustrated in FIG. 40 , a memory cell is provided in theregister 1196. For the memory cell of the register 1196, any of theabove-described transistors, the above-described memory device, or thelike can be used.

In the CPU illustrated in FIG. 40 , the register controller 1197 selectsoperation of retaining data in the register 1196 in accordance with aninstruction from the ALU 1191. That is, the register controller 1197selects whether data is retained by a flip-flop or by a capacitor in thememory cell included in the register 1196. When data retention by theflip-flop is selected, a power supply voltage is supplied to the memorycell in the register 1196. When data retention by the capacitor isselected, the data is rewritten in the capacitor, and supply of a powersupply voltage to the memory cell in the register 1196 can be stopped.

FIG. 41 is an example of a circuit diagram of a memory element 1200 thatcan be used as the register 1196. The memory element 1200 includes acircuit 1201 in which stored data is volatile when power supply isstopped, a circuit 1202 in which stored data is nonvolatile even whenpower supply is stopped, a switch 1203, a switch 1204, a logic element1206, a capacitor 1207, and a circuit 1220 having a selecting function.The circuit 1202 includes a capacitor 1208, a transistor 1209, and atransistor 1210. Note that the memory element 1200 may further includeanother element such as a diode, a resistor, or an inductor, as needed.

Here, the above-described memory device can be used as the circuit 1202.When supply of a power supply voltage to the memory element 1200 isstopped, GND (0 V) or a potential at which the transistor 1209 in thecircuit 1202 is turned off continues to be input to a gate of thetransistor 1209. For example, the gate of the transistor 1209 isgrounded through a load such as a resistor.

Shown here is an example in which the switch 1203 is a transistor 1213having one conductivity type (e.g., an n-channel transistor) and theswitch 1204 is a transistor 1214 having a conductivity type opposite tothe one conductivity type (e.g., a p-channel transistor). A firstterminal of the switch 1203 corresponds to one of a source and a drainof the transistor 1213, a second terminal of the switch 1203 correspondsto the other of the source and the drain of the transistor 1213, andconduction or non-conduction between the first terminal and the secondterminal of the switch 1203 (i.e., the on/off state of the transistor1213) is selected by a control signal RD input to a gate of thetransistor 1213. A first terminal of the switch 1204 corresponds to oneof a source and a drain of the transistor 1214, a second terminal of theswitch 1204 corresponds to the other of the source and the drain of thetransistor 1214, and conduction or non-conduction between the firstterminal and the second terminal of the switch 1204 (i.e., the on/offstate of the transistor 1214) is selected by the control signal RD inputto a gate of the transistor 1214.

One of a source and a drain of the transistor 1209 is electricallyconnected to one of a pair of electrodes of the capacitor 1208 and agate of the transistor 1210. Here, the connection portion is referred toas a node M2. One of a source and a drain of the transistor 1210 iselectrically connected to a line which can supply a low power supplypotential (e.g., a GND line), and the other thereof is electricallyconnected to the first terminal of the switch 1203 (the one of thesource and the drain of the transistor 1213).

The second terminal of the switch 1203 (the other of the source and thedrain of the transistor 1213) is electrically connected to the firstterminal of the switch 1204 (the one of the source and the drain of thetransistor 1214). The second terminal of the switch 1204 (the other ofthe source and the drain of the transistor 1214) is electricallyconnected to a line which can supply a power supply potential VDD. Thesecond terminal of the switch 1203 (the other of the source and thedrain of the transistor 1213), the first terminal of the switch 1204(the one of the source and the drain of the transistor 1214), an inputterminal of the logic element 1206, and one of a pair of electrodes ofthe capacitor 1207 are electrically connected to each other. Here, theconnection portion is referred to as a node M1. The other of the pair ofelectrodes of the capacitor 1207 can be supplied with a constantpotential. For example, the other of the pair of electrodes of thecapacitor 1207 can be supplied with a low power supply potential (e.g.,GND) or a high power supply potential (e.g., VDD). The other of the pairof electrodes of the capacitor 1207 is electrically connected to theline which can supply a low power supply potential (e.g., a GND line).The other of the pair of electrodes of the capacitor 1208 can besupplied with a constant potential. For example, the other of the pairof electrodes of the capacitor 1208 can be supplied with the low powersupply potential (e.g., GND) or the high power supply potential (e.g.,VDD). The other of the pair of electrodes of the capacitor 1208 iselectrically connected to the line which can supply a low power supplypotential (e.g., a GND line).

The capacitor 1207 and the capacitor 1208 are not necessarily providedas long as the parasitic capacitance of the transistor, the wiring, orthe like is actively utilized.

A control signal WE is input to the gate of the transistor 1209. As foreach of the switch 1203 and the switch 1204, a conduction state or anon-conduction state between the first terminal and the second terminalis selected by the control signal RD which is different from the controlsignal WE. When the first terminal and the second terminal of one of theswitches are in the conduction state, the first terminal and the secondterminal of the other of the switches are in the non-conduction state.

A signal corresponding to data retained in the circuit 1201 is input tothe other of the source and the drain of the transistor 1209. FIG. 41illustrates an example in which a signal output from the circuit 1201 isinput to the other of the source and the drain of the transistor 1209.The logic value of a signal output from the second terminal of theswitch 1203 (the other of the source and the drain of the transistor1213) is inverted by the logic element 1206, and the inverted signal isinput to the circuit 1201 through the circuit 1220.

In the example of FIG. 41 , a signal output from the second terminal ofthe switch 1203 (the other of the source and the drain of the transistor1213) is input to the circuit 1201 through the logic element 1206 andthe circuit 1220; however, one embodiment of the present invention isnot limited thereto. The signal output from the second terminal of theswitch 1203 (the other of the source and the drain of the transistor1213) may be input to the circuit 1201 without its logic value beinginverted. For example, in the case where the circuit 1201 includes anode in which a signal obtained by inversion of the logic value of asignal input from the input terminal is retained, the signal output fromthe second terminal of the switch 1203 (the other of the source and thedrain of the transistor 1213) can be input to the node.

In FIG. 41 , the transistors included in the memory element 1200 exceptthe transistor 1209 can each be a transistor in which a channel isformed in a film formed using a semiconductor other than an oxidesemiconductor or in the substrate 1190. For example, the transistor canbe a transistor whose channel is formed in a silicon film or a siliconsubstrate. Alternatively, all the transistors in the memory element 1200may be a transistor in which a channel is formed in an oxidesemiconductor. Further alternatively, in the memory element 1200, atransistor in which a channel is formed in an oxide semiconductor may beincluded besides the transistor 1209, and a transistor in which achannel is formed in a film formed using a semiconductor other than anoxide semiconductor or in the substrate 1190 can be used for the rest ofthe transistors.

As the circuit 1201 in FIG. 41 , for example, a flip-flop circuit can beused. As the logic element 1206, for example, an inverter or a clockedinverter can be used.

In a period during which the memory element 1200 is not supplied withthe power supply voltage, the semiconductor device of one embodiment ofthe present invention can retain data stored in the circuit 1201 by thecapacitor 1208 which is provided in the circuit 1202.

The off-state current of a transistor in which a channel is formed in anoxide semiconductor is extremely low. For example, the off-state currentof a transistor in which a channel is formed in an oxide semiconductoris significantly lower than that of a transistor in which a channel isformed in silicon having crystallinity. Thus, when the transistor isused as the transistor 1209, a signal held in the capacitor 1208 isretained for a long time also in a period during which the power supplyvoltage is not supplied to the memory element 1200. The memory element1200 can accordingly retain the stored content (data) also in a periodduring which the supply of the power supply voltage is stopped.

Since the above-described memory element performs pre-charge operationwith the switch 1203 and the switch 1204, the time required for thecircuit 1201 to retain original data again after the supply of the powersupply voltage is restarted can be shortened.

In the circuit 1202, a signal retained by the capacitor 1208 is input tothe gate of the transistor 1210. Therefore, after supply of the powersupply voltage to the memory element 1200 is restarted, the transistor1210 is brought into the on state or the off state depending on thesignal retained by the capacitor 1208, and a signal corresponding to thestate can be read from the circuit 1202. Consequently, an originalsignal can be accurately read even when a potential corresponding to thesignal retained by the capacitor 1208 varies to some degree.

By applying the above-described memory element 1200 to a memory devicesuch as a register or a cache memory included in a processor, data inthe memory device can be prevented from being lost owing to the stop ofthe supply of the power supply voltage. Furthermore, shortly after thesupply of the power supply voltage is restarted, the memory device canbe returned to the same state as that before the power supply isstopped. Therefore, the power supply can be stopped even for a shorttime in the processor or one or a plurality of logic circuits includedin the processor, resulting in lower power consumption.

Although the memory element 1200 is used in a CPU, the memory element1200 can also be used in an LSI such as a digital signal processor(DSP), a custom LSI, or a programmable logic device (PLD) and a radiofrequency (RF) device.

The structures described in this embodiment can be used in appropriatecombination with any of the structures described in the otherembodiments.

Embodiment 7

In this embodiment, a display device including the transistor of oneembodiment of the present invention and the like is described withreference to FIGS. 42A to 42C and FIGS. 43A and 43B.

<Configuration of Display Device>

Examples of a display element provided in the display device include aliquid crystal element (also referred to as a liquid crystal displayelement) and a light-emitting element (also referred to as alight-emitting display element). The light-emitting element includes, inits category, an element whose luminance is controlled by a current orvoltage, and specifically includes, in its category, an inorganicelectroluminescent (EL) element, an organic EL element, and the like. Adisplay device including an EL element (EL display device) and a displaydevice including a liquid crystal element (liquid crystal displaydevice) are described below as examples of the display device.

Note that the display device described below includes in its category apanel in which a display element is sealed and a module in which an ICsuch as a controller is mounted on the panel.

The display device described below refers to an image display device ora light source (including a lighting device). The display deviceincludes any of the following modules: a module provided with aconnector such as an FPC or TCP; a module in which a printed wiringboard is provided at the end of TCP; and a module in which an integratedcircuit (IC) is mounted directly on a display element by a COG method.

FIGS. 42A to 42C illustrate an example of an EL display device of oneembodiment of the present invention. FIG. 42A is a circuit diagram of apixel in an EL display device. FIG. 42B is a plan view showing the wholeof the EL display device. FIG. 42C is a cross-sectional view taken alongpart of dashed-dotted line M-N in FIG. 42B.

FIG. 42A illustrates an example of a circuit diagram of a pixel used inan EL display device.

Note that in this specification and the like, it might be possible forthose skilled in the art to constitute one embodiment of the inventioneven when portions to which all the terminals of an active element(e.g., a transistor or a diode), a passive element (e.g., a capacitor ora resistor), or the like are connected are not specified. In otherwords, one embodiment of the invention can be clear even when connectionportions are not specified. Furthermore, in the case where a connectionportion is disclosed in this specification and the like, it can bedetermined that one embodiment of the invention in which a connectionportion is not specified is disclosed in this specification and thelike, in some cases. Particularly in the case where the number ofportions to which a terminal is connected might be more than one, it isnot necessary to specify the portions to which the terminal isconnected. Therefore, it might be possible to constitute one embodimentof the invention by specifying only portions to which some of terminalsof an active element (e.g., a transistor or a diode), a passive element(e.g., a capacitor or a resistor), or the like are connected.

Note that in this specification and the like, it might be possible forthose skilled in the art to specify the invention when at least theconnection portion of a circuit is specified. Alternatively, it might bepossible for those skilled in the art to specify the invention when atleast a function of a circuit is specified. In other words, when afunction of a circuit is specified, one embodiment of the presentinvention can be clear. Furthermore, it can be determined that oneembodiment of the present invention whose function is specified isdisclosed in this specification and the like in some cases. Therefore,when a connection portion of a circuit is specified, the circuit isdisclosed as one embodiment of the invention even when a function is notspecified, and one embodiment of the invention can be constituted.Alternatively, when a function of a circuit is specified, the circuit isdisclosed as one embodiment of the invention even when a connectionportion is not specified, and one embodiment of the invention can beconstituted.

The EL display device illustrated in FIG. 42A includes a switchingelement 743, a transistor 741, a capacitor 742, and a light-emittingelement 719.

Note that FIG. 42A and the like each illustrate an example of a circuitstructure; therefore, a transistor can be provided additionally. Incontrast, for each node in FIG. 42A, it is possible not to provide anadditional transistor, switch, passive element, or the like.

A gate of the transistor 741 is electrically connected to one terminalof the switching element 743 and one electrode of the capacitor 742. Asource of the transistor 741 is electrically connected to the otherelectrode of the capacitor 742 and one electrode of the light-emittingelement 719. A drain of the transistor 741 is supplied with a powersupply potential VDD. The other terminal of the switching element 743 iselectrically connected to a signal line 744. A constant potential issupplied to the other electrode of the light-emitting element 719. Theconstant potential is a ground potential GND or a potential lower thanthe ground potential GND.

It is preferable to use a transistor as the switching element 743. Whenthe transistor is used as the switching element, the area of a pixel canbe reduced, so that the EL display device can have high resolution. Asthe switching element 743, a transistor formed through the same step asthe transistor 741 can be used, so that EL display devices can bemanufactured with high productivity. Note that as the transistor 741and/or the switching element 743, any of the above-described transistorscan be used, for example.

FIG. 42B is a plan view of the EL display device. The EL display deviceincludes a substrate 700, a substrate 750, a sealant 734, a drivercircuit 735, a driver circuit 736, a pixel 737, and an FPC 732. Thesealant 734 is provided between the substrate 700 and the substrate 750so as to surround the pixel 737, the driver circuit 735, and the drivercircuit 736. Note that the driver circuit 735 and/or the driver circuit736 may be provided outside the sealant 734.

FIG. 42C is a cross-sectional view of the EL display device taken alongpart of dashed-dotted line M-N in FIG. 42B.

FIG. 42C illustrates a structure of the transistor 741 including aconductor 704 a over the substrate 700; an insulator 712 a over theconductor 704 a; an insulator 712 b over the insulator 712 a;semiconductors 706 a and 706 b that are over the insulator 712 b andoverlap with the conductor 704 a; a conductor 716 a and a conductor 716b in contact with the semiconductors 706 a and 706 b; an insulator 718 aover the semiconductor 706 b, the conductor 716 a, and the conductor 716b; an insulator 718 b over the insulator 718 a; an insulator 718 c overthe insulator 718 b; and a conductor 714 a that is over the insulator718 c and overlaps with the semiconductor 706 b. Note that the structureof the transistor 741 is just an example; the transistor 741 may have astructure different from that illustrated in FIG. 42C.

Thus, in the transistor 741 illustrated in FIG. 42C, the conductor 704 aserves as a gate electrode, the insulator 712 a and the insulator 712 bserve as a gate insulator, the conductor 716 a serves as a sourceelectrode, the conductor 716 b serves as a drain electrode, theinsulator 718 a, the insulator 718 b, and the insulator 718 c serve as agate insulator, and the conductor 714 a serves as a gate electrode. Notethat in some cases, electrical characteristics of the semiconductors 706a and 706 b change if light enters the semiconductors 706 a and 706 b.To prevent this, it is preferable that one or more of the conductor 704a, the conductor 716 a, the conductor 716 b, and the conductor 714 ahave a light-blocking property.

Note that the interface between the insulator 718 a and the insulator718 b is indicated by a broken line. This means that the boundarybetween them is not clear in some cases. For example, in the case wherethe insulator 718 a and the insulator 718 b are formed using insulatorsof the same kind, the insulator 718 a and the insulator 718 b are notdistinguished from each other in some cases depending on an observationmethod.

FIG. 42C illustrates a structure of the capacitor 742 including aconductor 704 b over the substrate; the insulator 712 a over theconductor 704 b; the insulator 712 b over the insulator 712 a; theconductor 716 a that is over the insulator 712 b and overlaps with theconductor 704 b; the insulator 718 a over the conductor 716 a; theinsulator 718 b over the insulator 718 a; the insulator 718 c over theinsulator 718 b; and a conductor 714 b that is over the insulator 718 cand overlaps with the conductor 716 a. In this structure, part of theinsulator 718 a and part of the insulator 718 b are removed in a regionwhere the conductor 716 a and the conductor 714 b overlap with eachother.

In the capacitor 742, each of the conductor 704 b and the conductor 714b functions as one electrode, and the conductor 716 a functions as theother electrode.

Thus, the capacitor 742 can be formed using a film of the transistor741. The conductor 704 a and the conductor 704 b are preferablyconductors of the same kind, in which case the conductor 704 a and theconductor 704 b can be formed through the same step. Furthermore, theconductor 714 a and the conductor 714 b are preferably conductors of thesame kind, in which case the conductor 714 a and the conductor 714 b canbe formed through the same step.

The capacitor 742 illustrated in FIG. 42C has a large capacitance perarea occupied by the capacitor. Therefore, the EL display deviceillustrated in FIG. 42C has high display quality. Note that although thecapacitor 742 illustrated in FIG. 42C has the structure in which thepart of the insulator 718 a and the part of the insulator 718 b areremoved to reduce the thickness of the region where the conductor 716 aand the conductor 714 b overlap with each other, the structure of thecapacitor according to one embodiment of the present invention is notlimited to the structure. For example, a structure in which part of theinsulator 718 c is removed to reduce the thickness of the region wherethe conductor 716 a and the conductor 714 b overlap with each other maybe used.

An insulator 720 is provided over the transistor 741 and the capacitor742. Here, the insulator 720 may have an opening reaching the conductor716 a that serves as the source electrode of the transistor 741. Aconductor 781 is provided over the insulator 720. The conductor 781 maybe electrically connected to the transistor 741 through the opening inthe insulator 720.

A partition wall 784 having an opening reaching the conductor 781 isprovided over the conductor 781. A light-emitting layer 782 in contactwith the conductor 781 through the opening provided in the partitionwall 784 is provided over the partition wall 784. A conductor 783 isprovided over the light-emitting layer 782. A region where the conductor781, the light-emitting layer 782, and the conductor 783 overlap withone another functions as the light-emitting element 719.

So far, examples of the EL display device are described. Next, anexample of a liquid crystal display device is described.

FIG. 43A is a circuit diagram illustrating a configuration example of apixel of a liquid crystal display device. A pixel shown in FIGS. 43A and43B includes a transistor 751, a capacitor 752, and an element (liquidcrystal element) 753 in which a space between a pair of electrodes isfilled with a liquid crystal.

One of a source and a drain of the transistor 751 is electricallyconnected to a signal line 755, and a gate of the transistor 751 iselectrically connected to a scan line 754.

One electrode of the capacitor 752 is electrically connected to theother of the source and the drain of the transistor 751, and the otherelectrode of the capacitor 752 is electrically connected to a wiring towhich a common potential is supplied.

One electrode of the liquid crystal element 753 is electricallyconnected to the other of the source and the drain of the transistor751, and the other electrode of the liquid crystal element 753 iselectrically connected to a wiring to which a common potential issupplied. The common potential supplied to the wiring electricallyconnected to the other electrode of the capacitor 752 may be differentfrom that supplied to the other electrode of the liquid crystal element753.

Note that the description of the liquid crystal display device is madeon the assumption that the plan view of the liquid crystal displaydevice is similar to that of the EL display device. FIG. 43B is across-sectional view of the liquid crystal display device taken alongdashed-dotted line M-N in FIG. 42B. In FIG. 43B, the FPC 732 isconnected to the wiring 733 a via the terminal 731. Note that the wiring733 a may be formed using the same kind of conductor as the conductor ofthe transistor 751 or using the same kind of semiconductor as thesemiconductor of the transistor 751.

For the transistor 751, the description of the transistor 741 isreferred to. For the capacitor 752, the description of the capacitor 742is referred to. Note that the structure of the capacitor 752 in FIG. 43Bcorresponds to, but is not limited to, the structure of the capacitor742 in FIG. 42C.

Note that in the case where an oxide semiconductor is used as thesemiconductor of the transistor 751, the off-state current of thetransistor 751 can be extremely small. Therefore, an electric chargeheld in the capacitor 752 is unlikely to leak, so that the voltageapplied to the liquid crystal element 753 can be maintained for a longtime. Accordingly, the transistor 751 can be kept off during a period inwhich moving images with few motions or a still image are/is displayed,whereby power for the operation of the transistor 751 can be saved inthat period; accordingly a liquid crystal display device with low powerconsumption can be provided. Furthermore, the area occupied by thecapacitor 752 can be reduced; thus, a liquid crystal display device witha high aperture ratio or a high-resolution liquid crystal display devicecan be provided.

An insulator 721 is provided over the transistor 751 and the capacitor752. The insulator 721 has an opening reaching the transistor 751. Aconductor 791 is provided over the insulator 721. The conductor 791 iselectrically connected to the transistor 751 through the opening in theinsulator 721.

An insulator 792 functioning as an alignment film is provided over theconductor 791. A liquid crystal layer 793 is provided over the insulator792. An insulator 794 functioning as an alignment film is provided overthe liquid crystal layer 793. A spacer 795 is provided over theinsulator 794. A conductor 796 is provided over the spacer 795 and theinsulator 794. A substrate 797 is provided over the conductor 796.

Owing to the above-described structure, a display device including acapacitor occupying a small area, a display device with high displayquality, or a high-resolution display device can be provided.

For example, in this specification and the like, a display element, adisplay device which is a device including a display element, alight-emitting element, and a light-emitting device which is a deviceincluding a light-emitting element can employ various modes or caninclude various elements. For example, the display element, the displaydevice, the light-emitting element, or the light-emitting deviceincludes at least one of a light-emitting diode (LED) for white, red,green, blue, or the like, a transistor (a transistor that emits lightdepending on current), an electron emitter, a liquid crystal element,electronic ink, an electrophoretic element, a grating light valve (GLV),a plasma display panel (PDP), a display element using micro electromechanical systems (MEMS), a digital micromirror device (DMD), a digitalmicro shutter (DMS), an interferometric modulator display (IMOD)element, a MEMS shutter display element, an optical-interference-typeMEMS display element, an electrowetting element, a piezoelectric ceramicdisplay, and a display element including a carbon nanotube. Displaymedia whose contrast, luminance, reflectivity, transmittance, or thelike is changed by electrical or magnetic effect may be included.

Note that examples of display devices having EL elements include an ELdisplay. Examples of a display device including an electron emitterinclude a field emission display (FED), an SED-type flat panel display(SED: surface-conduction electron-emitter display), and the like.Examples of display devices including liquid crystal elements include aliquid crystal display (e.g., a transmissive liquid crystal display, atransflective liquid crystal display, a reflective liquid crystaldisplay, a direct-view liquid crystal display, or a projection liquidcrystal display). Examples of a display device including electronic ink,Electronic Liquid Powder (registered trademark), or an electrophoreticelement include electronic paper. In the case of a transflective liquidcrystal display or a reflective liquid crystal display, some of or allof pixel electrodes function as reflective electrodes. For example, someor all of pixel electrodes are formed to contain aluminum, silver, orthe like. In such a case, a memory circuit such as an SRAM can beprovided under the reflective electrodes. Thus, the power consumptioncan be further reduced.

Note that in the case of using an LED, graphene or graphite may beprovided under an electrode or a nitride semiconductor of the LED.Graphene or graphite may be a multilayer film in which a plurality oflayers are stacked. As described above, provision of graphene orgraphite enables easy formation of a nitride semiconductor thereover,such as an n-type GaN semiconductor including crystals. Furthermore, ap-type GaN semiconductor including crystals or the like can be providedthereover, and thus the LED can be formed. Note that an AlN layer may beprovided between the n-type GaN semiconductor including crystals andgraphene or graphite. The GaN semiconductors included in the LED may beformed by MOCVD. Note that when the graphene is provided, the GaNsemiconductors included in the LED can also be formed by a sputteringmethod.

The structures described in this embodiment can be used in appropriatecombination with any of the structures described in the otherembodiments.

Embodiment 8

In this embodiment, electronic devices each including the transistor orthe like of one embodiment of the present invention are described.

<Electronic Device>

The semiconductor device of one embodiment of the present invention canbe used for display devices, personal computers, or image reproducingdevices provided with recording media (typically, devices whichreproduce the content of recording media such as digital versatile discs(DVDs) and have displays for displaying the reproduced images). Otherexamples of electronic devices that can be equipped with thesemiconductor device of one embodiment of the present invention aremobile phones, game machines including portable game consoles, portabledata terminals, e-book readers, cameras such as video cameras anddigital still cameras, goggle-type displays (head mounted displays),navigation systems, audio reproducing devices (e.g., car audio systemsand digital audio players), copiers, facsimiles, printers, multifunctionprinters, automated teller machines (ATM), and vending machines. FIGS.44A to 44F illustrate specific examples of these electronic devices.

FIG. 44A illustrates a portable game console including a housing 901, ahousing 902, a display portion 903, a display portion 904, a microphone905, a speaker 906, an operation key 907, a stylus 908, and the like.Although the portable game console in FIG. 44A has the two displayportions 903 and 904, the number of display portions included in aportable game console is not limited to this.

FIG. 44B illustrates a portable data terminal including a first housing911, a second housing 912, a first display portion 913, a second displayportion 914, a joint 915, an operation key 916, and the like. The firstdisplay portion 913 is provided in the first housing 911, and the seconddisplay portion 914 is provided in the second housing 912. The firsthousing 911 and the second housing 912 are connected to each other withthe joint 915, and the angle between the first housing 911 and thesecond housing 912 can be changed with the joint 915. An image on thefirst display portion 913 may be switched in accordance with the angleat the joint 915 between the first housing 911 and the second housing912. A display device with a position input function may be used as atleast one of the first display portion 913 and the second displayportion 914. Note that the position input function can be added byproviding a touch panel in a display device. Alternatively, the positioninput function can be added by providing a photoelectric conversionelement called a photosensor in a pixel portion of a display device.

FIG. 44C illustrates a notebook personal computer, which includes ahousing 921, a display portion 922, a keyboard 923, a pointing device924, and the like.

FIG. 44D illustrates an electric refrigerator-freezer, which includes ahousing 931, a door for a refrigerator 932, a door for a freezer 933,and the like.

FIG. 44E illustrates a video camera, which includes a first housing 941,a second housing 942, a display portion 943, operation keys 944, a lens945, a joint 946, and the like. The operation keys 944 and the lens 945are provided for the first housing 941, and the display portion 943 isprovided for the second housing 942. The first housing 941 and thesecond housing 942 are connected to each other with the joint 946, andthe angle between the first housing 941 and the second housing 942 canbe changed with the joint 946. Images displayed on the display portion943 may be switched in accordance with the angle at the joint 946between the first housing 941 and the second housing 942.

FIG. 44F illustrates a car including a car body 951, wheels 952, adashboard 953, lights 954, and the like.

This embodiment of the present invention has been described in the aboveembodiments. Note that one embodiment of the present invention is notlimited thereto. That is, various embodiments of the invention aredescribed in this embodiment and the like, and one embodiment of thepresent invention is not limited to a particular embodiment. Forexample, an example in which a channel formation region, source anddrain regions, and the like of a transistor include an oxidesemiconductor is described as one embodiment of the present invention;however, one embodiment of the present invention is not limited to thisexample. Alternatively, depending on circumstances or conditions,various semiconductors may be included in various transistors, a channelformation region of a transistor, a source region or a drain region of atransistor, or the like of one embodiment of the present invention.Depending on circumstances or conditions, at least one of silicon,germanium, silicon germanium, silicon carbide, gallium arsenide,aluminum gallium arsenide, indium phosphide, gallium nitride, an organicsemiconductor, and the like may be included in various transistors, achannel formation region of a transistor, a source region or a drainregion of a transistor, or the like of one embodiment of the presentinvention. Alternatively, depending on circumstances or conditions, anoxide semiconductor is not necessarily included in various transistors,a channel formation region of a transistor, a source region or a drainregion of a transistor, or the like of one embodiment of the presentinvention, for example.

Example 1

In this example, samples in each of which a silicon oxide film, ahafnium oxide film, and a silicon oxide film containing fluorine werestacked over a silicon substrate were formed and analyzed by TDS andESR, and the analysis results will be described. For the TDS analysis,three samples 1A to 1C were formed. The substrate temperatures forforming the silicon oxide films containing fluorine of the samples 1A,1B, and 1C were 350° C., 400° C., and 445° C., respectively.Furthermore, for the ESR analysis, samples 1A-1 to 1C-1 that correspondto the samples 1A to 1C not further subjected to heat treatment (i.e.,the samples 1A-1 to 1C-1 are identical to the samples 1A to 1C); samples1A-2 to 1C-2 that correspond to the samples 1A to 1C subjected to heattreatment at 410° C.; samples 1A-3 to 1C-3 that correspond to thesamples 1A to 1C subjected to heat treatment at 490° C.; and samples1A-4 to 1C-4 that correspond to the samples 1A to 1C subjected to heattreatment at 550° C. were formed.

A method for forming the samples used in the TDS analysis is described.First, by thermal oxidation of a silicon wafer, a 100-nm-thick siliconoxide film was formed on a surface of the silicon wafer. The thermaloxidation was performed at 950° C. in an oxygen atmosphere containingHCl at 3 volume % for 4 hours.

Next, a 20-nm-thick hafnium oxide film was formed over the silicon oxidefilm by an ALD method. In the film formation by an ALD method, thesubstrate temperature was 200° C., and a source gas obtained byvaporizing a solid containing tetrakis(dimethylamido)hafnium (TDMAH) andan O₃ gas) that was an oxidizer were used.

Then, a 30-nm-thick silicon oxide film containing fluorine was formedover the hafnium oxide film by a PECVD method. Before the deposition ofthe silicon oxide film containing fluorine, pretreatment for letting 200sccm of SiH₄ flow for 20 seconds was performed. The depositionconditions were as follows: 1.5 sccm of SiF₄, 1000 sccm of N₂O, and 1000sccm of Ar were used as deposition gases; RF power source frequency was60 MHz; RF power was 800 W; and deposition pressure was 133 Pa. Thesubstrate temperatures for the sample 1A, the sample 1B, and the sample1C were 350° C., 400° C., and 445° C., respectively.

The samples 1A to 1C formed in the above manner were analyzed by TDS andthe results are shown in FIGS. 45A to 45D, FIGS. 46A to 46D, and FIGS.47A to 47D, respectively. Note that in the TDS analysis, the amounts ofreleased gases with a mass-to-charge ratios m/z of 2, 18, 19, and 32which correspond to a hydrogen molecule, a water molecule, a fluorineatom, and an oxygen molecule, respectively, were measured. FIG. 45A,FIG. 46A, and FIG. 47A show the measurement results of hydrogen; FIG.45B, FIG. 46B, and FIG. 47B show those of water; FIG. 45C, FIG. 46C, andFIG. 47C show those of fluorine; and FIG. 45D, FIG. 46D, and FIG. 47Dshow those of oxygen. In each of FIGS. 45A to 45D, FIGS. 46A to 46D, andFIGS. 47A to 47D, the horizontal axis represents substrate heatingtemperature [° C.] and the vertical axis represents intensityproportional to the amount of a released gas with a mass-to-chargeratio.

The numbers of hydrogen molecules, water molecules, and oxygen moleculesreleased from the samples 1A to 1C, which are calculated from theprofiles shown in FIGS. 45A, 45B, and 45D, FIGS. 46A, 46B, and 46D, andFIGS. 47A, 47B, and 47D are shown in Table 1. Note that the numbers ofreleased hydrogen molecules, released water molecules, and releasedoxygen molecules were calculated on the assumption that the backgroundvalues of the TDS profiles were the minimum values. Table 1 also showsthe number of molecules released from a reference sample 1 in which asilicon oxide film was formed by a PECVD method using SiH₄ at asubstrate temperature of 400° C. instead of the silicon oxide filmcontaining fluorine and the number of molecules released from areference sample 2 in which a silicon oxide film was formed by a PECVDmethod using SiH₄ at a substrate temperature of 500° C. instead of thesilicon oxide film containing fluorine.

TABLE 1 Sample Sample Sample Reference Reference 1A 1B 1C sample 1sample 2 Hydrogen 1.20E+15 8.58E+14 8.23E+14 1.18E+15 7.03E+14[molecule/ cm²] Water 1.78E+15 1.23E+15 1.08E+15 1.42E+16 3.19E+15[molecule/ cm²] Oxygen 8.33E+13 7.02E+13 8.72E+13 1.50E+14 5.41E+13[molecule/ cm²]

As shown in Table 1, the number of hydrogen molecules released from thesample 1A was 1.20×10¹⁵ molecules/cm², and the number of water moleculesreleased from the sample 1A was 1.78×10¹⁵ molecules/cm². The number ofhydrogen molecules released from the sample 1B was 8.58×10¹⁴molecules/cm², and the number of water molecules released from thesample 1B was 1.23×10¹⁵ molecules/cm². The number of hydrogen moleculesreleased from the sample 1C was 8.23×10¹⁴ molecules/cm², and the numberof water molecules released from the sample 1C was 1.08×10¹⁵molecules/cm².

From the reference sample 1 in which the silicon oxide film was formedat a substrate temperature of 400° C., the number of released hydrogenmolecules was 1.18×10¹⁵ molecules/cm² and the number of released watermolecules was 1.42×10¹⁶ molecules/cm². From the reference sample 2 inwhich the silicon oxide film was formed at a substrate temperature of500° C., the number of released hydrogen molecules was 7.03×10¹⁴molecules/cm² and the number of released water molecules was 3.19×10¹⁵molecules/cm². Therefore, the numbers of hydrogen molecules and watermolecules, particularly the number of water molecules, released from thereference sample 2 (substrate temperature: 500° C.) can be significantlyreduced as compared with the reference sample 1 (substrate temperature:400° C.).

Although the substrate temperatures for the samples 1A to 1C were from350° C. to 445° C., the number of water molecules released from each ofthe samples 1A to 1C was smaller than that from the reference sample 2for which the substrate temperature was 500° C. In particular, thenumber of water molecules released from each of the samples 1 A to 1Cwas suppressed to be approximately smaller than or equal to a tenth ofthe number of water molecules released from the reference sample 1(substrate temperature: 400° C.), which was a pronounced effect. Thenumber of hydrogen molecules released from the sample 1A wassubstantially equal to that from the reference sample 1 (substratetemperature: 400° C.), and the number of hydrogen molecules releasedfrom each of the samples 1B and 1C was substantially equal to that fromthe reference sample 2 (substrate temperature: 500° C.). When thereference sample 1 and the reference sample 2 were compared, adifference in the number of released hydrogen molecules as large as adifference in the number of released water molecules was not found.

Although the samples 1A to 1C described in this example were formedunder the relatively low temperature conditions (substrate temperatureranging from 350° C. to 445° C.), impurities such as water and hydrogenin the samples 1A to 1C were able to be reduced to the same level as inthe reference sample 2 (substrate temperature: 500° C.).

In TDS analysis, the number of hydrogen molecules released from, forexample, the stacked film of the insulator 105, the insulator 103, andthe insulator 104 which is provided in contact with a bottom surface ofthe oxide semiconductor and which functions as the gate insulating filmin the transistor described in the above embodiments is preferably lessthan or equal to 1.2×10¹⁵ molecules/cm², and more preferably less thanor equal to 9.0×10¹⁴ molecules/cm². Similarly, in TDS analysis, thenumber of water molecules released from the stacked film is preferablyless than or equal to 1.4×10¹⁶ molecules/cm², more preferably less thanor equal to 4.0×10¹⁵ molecules/cm², and further more preferably lessthan or equal to 2.0×10¹⁵ molecules/cm².

Note that the stacked film of the insulator 105, the insulator 103, andthe insulator 104 is formed as each sample in this example; therefore,the number of water molecules and the number of hydrogen moleculesreleased from each of the samples 1A to 1C correspond to the sum of thenumber of molecules released from the insulator 104 and the number ofmolecules that are released from the insulator 105 and the insulator 103and then pass through the insulator 104. Accordingly, the number ofwater molecules and the number of hydrogen molecules released from onlythe insulator 104 are each presumably close to or smaller than thenumber of water molecules or the number of hydrogen molecules releasedfrom the stacked film in this example.

As described above, the stacked films of the samples 1A to 1C can beformed at relatively low substrate temperatures ranging from 350° C. to445° C. by a PECVD method. Even in the stacked film, water, hydrogen,and the like can be sufficiently reduced as described above.

As shown in Table 1 and the like, release of oxygen molecules from thesamples 1A to 1C was observed in TDS analysis. This means that byproviding the stacked film of any of the samples 1A to 1C under theoxide semiconductor, oxygen can be supplied to the oxide semiconductor.This is probably because oxygen in the silicon oxide containing fluorineis replaced with fluorine by the heat treatment, so that the oxygen isreleased (SiO+F→SiF+0).

As shown in FIG. 45C, FIG. 46C, and FIG. 47C, release of fluorine fromthe stacked film of each of the samples 1A to 1C was observed in TDSanalysis.

Next, a method for forming the samples used in the ESR analysis isdescribed. First, the samples 1A-1 to 1A-4 with the same structure asthe sample 1A were prepared. Similarly, the samples 1B-1 to 1B-4 withthe same structure as the sample 1B were prepared. Moreover, the samples1C-1 to 1C-4 with the same structure as the sample 1C were prepared.

Then, the samples 1A-2, 1B-2, and 1C-2 were subjected to heat treatmentin an oxygen atmosphere at 410° C. for an hour. The samples 1A-3, 1B-3,and 1C-3 were subjected to heat treatment in an oxygen atmosphere at490° C. for an hour. The samples 1A-4, 1B-4, and 1C-4 were subjected toheat treatment in an oxygen atmosphere at 550° C. for an hour. Note thatthe samples 1A-1, 1B-1, and 1C-1 were not subjected to heat treatment.

The samples formed in the above manner were analyzed by ESR and theresults are shown in FIG. 48 . The ESR analysis was performed under thefollowing conditions: the measurement temperature was 10 K; themicrowave power was 0.1 mW; and the frequency was 9.56 GHz.

In this example, whether the stacked films with the above structurescontain NO₂ described in the above embodiment was examined by ESRanalysis. The spin densities in oxide semiconductor films were evaluatedby ESR. When silicon oxide contains NO₂, in an ESR spectrum at 100 K orlower, a first absorption line that appears at a g-factor of greaterthan or equal to 2.037 and less than or equal to 2.039, a secondabsorption line that appears at a g-factor of greater than or equal to2.001 and less than or equal to 2.003, and a signal including a thirdabsorption line that appears at a g-factor of greater than or equal to1.964 and less than or equal to 1.966 are observed in some cases. Thedistance between the first and second absorption lines and the distancebetween the second and third absorption lines that are obtained by ESRmeasurement using an X-band are each approximately 5 mT. Therefore,silicon oxide containing a small amount of nitrogen oxide had a spindensity derived from NO₂ of less than 1×10¹⁸ spins/cm³.

In FIG. 48 , the horizontal axis represents the samples and the verticalaxis represents the spin density [spins/cm³] of signals corresponding tothe first to third absorption lines.

As shown in FIG. 48 , in every sample, the spin density of signalscorresponding to the first to third absorption lines is significantlylow, which implies that NO₂ hardly exist. Since the spin densities ofthe samples other than the samples 1A-1, 1B-1, 1C-1, and 1C-4 were lowerthan the lower limit of the detection, the heat treatment in an oxygenatmosphere seems to have a tendency to further reduce NO₂ in the stackedfilm.

The stacked film with the structure described in this example is usedas, for example, the insulators 105, 103, and 104 of the transistordescribed in the above embodiment, in which case NO₂ in the insulatorsis reduced; therefore, the transistor can have stable electricalcharacteristics.

Example 2

In this example, a sample 2A was formed as a transistor of oneembodiment of the present invention in such a manner that a stacked filmthat was in contact with the bottom surface of the oxide semiconductorand that functioned as the gate insulating film was formed and thecontent of hydrogen in the stacked film was reduced. As a comparativeexample, a sample 2B in which the content of hydrogen in the stackedfilm was not reduced was formed. The electrical characteristics andreliability of the transistors of the samples 2A and 2B were examined.

FIGS. 1A to 1D and other drawings can be referred to for the structureof the transistor, and FIGS. 13A to 13H, FIGS. 14A to 14F, and FIGS. 15Aand 15B and other drawings can be referred to for the method forfabricating the transistor.

First, a silicon substrate in which a 100-nm-thick silicon oxide film, a280-nm-thick silicon nitride oxide film, a 300-nm-thick silicon oxidefilm, and a 300-nm-thick silicon oxide film were stacked in this orderwas prepared as the substrate 100.

Next, a 150-nm-thick aluminum oxide film was formed as the insulator 101by a sputtering method.

Next, a 150-nm-thick tungsten film was formed by a sputtering method. Aresist was formed over the tungsten film and processing was performedusing the resist, whereby the conductor 102 was formed.

Then, a 10-nm-thick silicon oxide film was formed as the insulator 105by a PECVD method.

Next, a 20-nm-thick hafnium oxide film was formed as the insulator 103by an ALD method. In the film formation by an ALD method, the substratetemperature was 200° C., and a gas obtained by vaporizing a solidcontaining tetrakis(dimethylamido)hafnium (TDMAH) was used as a sourcegas and an O₃ gas) was used as an oxidizer.

Then, a 30-nm-thick silicon oxide film was formed as the insulator 104by a PECVD method. As the insulator 104 of the sample 2A, a siliconoxide film containing fluorine was formed with the use of SiF₄ as adeposition gas. As the insulator 104 of the sample 2B, a silicon oxidefilm was formed with the use of SiH₄ as a deposition gas.

For the sample 2A, before the deposition of the silicon oxide filmcontaining fluorine, pretreatment for letting SiH₄ flow at 200 sccm for20 seconds was performed. The deposition conditions for the insulator104 of the sample 2A were as follows: 1.5 sccm of SiF₄, 1000 sccm ofN₂O, and 1000 sccm of Ar were used as deposition gases; RF power sourcefrequency was 60 MHz; RF power was 800 W; deposition pressure was 133Pa; and the substrate temperature was 400° C.

The deposition conditions for the insulator 104 of the sample 2B were asfollows: 1 sccm of SiH₄ and 800 sccm of N₂O were used as depositiongases; RF power source frequency was 60 MHz; RF power was 150 W;deposition pressure was 40 Pa; and the substrate temperature was 400° C.

Next, heat treatment was performed at 410° C. in an oxygen atmospherefor an hour.

Next, a 40-nm-thick In—Ga—Zn oxide film was formed by a DC sputteringmethod to form an oxide to be the insulator 106 a using a target havingan atomic ratio of In:Ga:Zn=1:3:4 and deposition gases of an argon gasat 40 sccm and an oxygen gas at 5 sccm. A deposition pressure was 0.7 Pa(measured by Miniature Gauge MG-2 manufactured by CANON ANELVACORPORATION). A deposition power was 500 W. A substrate temperature was200° C. A distance between the target and the substrate was 60 mm.

Next, a 20-nm-thick In—Ga—Zn oxide film was formed by a DC sputteringmethod to form an oxide to be the semiconductor 106 b using a targethaving an atomic ratio of In:Ga:Zn=1:1:1 and deposition gases of anargon gas at 30 sccm and an oxygen gas at 15 sccm. A deposition pressurewas 0.7 Pa (measured by Miniature Gauge MG-2 manufactured by CANONANELVA CORPORATION). A deposition power was 500 W. A substratetemperature was 300° C. A distance between the target and the substratewas 60 mm.

Next, heat treatment was performed at 400° C. under a nitrogenatmosphere for an hour. In addition, heat treatment was performed at400° C. under an oxygen atmosphere for an hour.

Then, a 50-nm-thick tungsten film was formed by a DC sputtering methodas a conductor to be the conductors 108 a and 108 b.

A resist was then formed over the conductor and processing was performedusing the resist, whereby the conductors 108 a and 108 b were formed.

Next, the above oxide was processed using the resist and the conductors108 a and 108 b to form the insulator 106 a and the semiconductor 106 b.

Next, a 5-nm-thick In—Ga—Zn oxide film was formed by a DC sputteringmethod to form an oxide to be the insulator 106 c using a target havingan atomic ratio of In:Ga:Zn=1:3:2 and deposition gases of an argon gasat 30 sccm and an oxygen gas at 15 sccm. A deposition pressure was 0.7Pa. A deposition power was 500 W. A substrate temperature was 200° C. Adistance between the target and the substrate was 60 mm.

A 13-nm-thick silicon oxynitride film was formed as an oxynitride to bethe insulator 112 by a PECVD method.

Then, as a conductor to be the conductor 114, a 30-nm-thick titaniumnitride film and a 135-nm-thick tungsten film were formed in this orderby a DC sputtering method. A resist was then formed over the conductorand processing was performed using the resist, whereby the conductor 114was formed.

Next, the above oxide and oxynitride were processed using the resistinto the insulator 106 c and the insulator 112.

After that, a 140-nm-thick aluminum oxide film was formed by an RFsputtering method as the insulator 116, using 25 sccm of an argon gasand 25 sccm of an oxygen gas as deposition gases. A deposition pressurewas 0.4 Pa. A deposition power was 2500 W. A substrate temperature was250° C. A distance between the target and the substrate was 60 mm.

Next, heat treatment was performed at 400° C. in an oxygen atmospherefor an hour.

Then, a 300-nm-thick silicon oxynitride film was formed by a PECVDmethod.

Next, a 50-nm-thick titanium film, a 200-nm-thick aluminum film, and a50-nm-thick titanium film were formed in this order by a DC sputteringmethod. The films were processed using a resist to form the conductor120 a and the conductor 120 b.

In this manner, the transistor having a channel length L of 0.18 μm anda channel width W of 0.27 μm was fabricated.

The I_(d)-V_(g) characteristics (drain current-gate voltagecharacteristics) of the samples 2A and 2B were measured. The measurementof the I_(d)-V_(g) characteristics was performed at a back gate voltageof 0 V. Other measurement conditions were as follows: the drain voltagewas 0.1 V or 1.8 V, and the gate voltage was swept from −3.0 V to 3.0 Vin increments of 0.1 V.

FIGS. 49A and 49B show I_(d)-V_(g) characteristics of the samples 2A and2B. In each of FIGS. 49A and 49B, the horizontal axis represents gatevoltage V_(g) [V], the left vertical axis represents drain current I_(d)[A], and the right vertical axis represents field-effect mobility μFE[cm²/Vs]. In each of FIGS. 49A and 49B, a solid line denotes draincurrent and a dashed line denotes field-effect mobility.

As shown in FIG. 49B, the sample 2B in which the insulator 104 wasformed using SiH₄ and a large number of water molecules and hydrogenmolecules were contained in the film exhibits variations in transistorcharacteristics and the gate voltages at the rising of drain currentshifted, as a whole, in a negative direction. In contrast, the sample 2Ain which the insulator 104 was formed using SiF₄ and the number of watermolecules and hydrogen molecules in the film was reduced exhibitsfavorable electrical characteristics as shown in FIG. 49A. In the sample2A, when the back-gate voltage was 0 V and the drain voltage V_(d) was0.1 V, both the field-effect mobility and the subthreshold swing value(S value) were favorable, which were 3.5 cm²/Vs and 124.2 mV/dec,respectively.

Then, the threshold voltage V_(th) and Shift of the transistor of thesample 2A were calculated.

The threshold voltage and Shift in this specification are described. Thethreshold voltage is defined as, in the V_(g)-I_(d) curve where thehorizontal axis represents gate voltage V_(g) [V] and the vertical axisrepresents the square root of drain current I_(d) ^(1/2) [A], a gatevoltage at the intersection point of the line of I_(d) ^(1/2)=0 (V_(g)axis) and the tangent to the curve at a point where the slope of thecurve is the steepest. Note that here, the threshold voltage iscalculated with a drain voltage V_(d) of 1.8 V.

Note that the gate voltage at the rising of drain current in I_(d)-V_(g)characteristics is referred to as Shift. Furthermore, Shift in thisspecification is defined as, in the V_(g)-I_(d) curve where thehorizontal axis represents the gate voltage V_(g) [V] and the verticalaxis represents the logarithm of the drain current I_(d) [A], a gatevoltage at the intersection point of the line of I_(d)=1.0×10⁻¹² [A] andthe tangent to the curve at a point where the slope of the curve is thesteepest. Note that here, Shift is calculated with a drain voltage V_(d)of 1.8 V.

In the sample 2A, when the back gate voltage was 0 V, the thresholdvoltage and Shift of the transistor were 1.13 V and 0.17 V,respectively, which means that the transistor had normally-offelectrical characteristics even when the back gate voltage was 0 V.

Here, the stacked film of the insulators 105, 103, and 104 in the sample2A corresponds to that in the sample 1A in Example 1; and the stackedfilm of the insulators 105, 103, and 104 in the sample 2B corresponds tothat in the reference sample 1 in Example 1. By setting the number ofwater molecules or hydrogen molecules (particularly water molecules)released from the stacked film of the insulators 105, 103, and 104within the range described in Example 1, favorable transistorcharacteristics were able to be obtained. Moreover, although the heatingtemperature in the process of forming the transistor was approximately400° C., favorable transistor characteristics were able to be obtained.

The above results indicate that formation of the insulator 104 incontact with the bottom surface of the oxide semiconductor by a PECVDmethod using SiF₄ in order to make the amount of water, hydrogen, andthe like in the insulator 104 small can reduce defect states formed bysupply of water, hydrogen, and the like from the insulator 104 to thesemiconductor 106 b or the like. The use of such an oxide semiconductorwith a reduced density of defect states makes it possible to provide atransistor with stable electrical characteristics.

Next, samples 2A-1 to 2A-3, each of which has the same structure as thesample 2A, were formed by varying the temperature of the heat treatmentafter the formation of the insulator 104 and the temperature of the heattreatment after the formation of the oxide film to be the semiconductor106 b. Variations in Shift were measured at 25 points on a substratesurface of each sample. The temperature of the heat treatment after theformation of the insulator 104 was 550° C. for the sample 2A-1, 490° C.for the sample 2A-2, and 410° C. for the sample 2A-3. The temperature ofthe heat treatment after the formation of the oxide film to be thesemiconductor 106 b was 550° C. for the sample 2A-1, 450° C. for thesample 2A-2, and 400° C. for the sample 2A-3. That is, the heattreatment conditions of the sample 2A-3 were the same as those of thesample 2A.

The measurement results are shown in FIG. 50 . In FIG. 50 , thehorizontal axis represents the samples 2A-1 to 2A-3 and the verticalaxis represents Shift [V].

As shown in FIG. 50 , variations in Shift in the substrate surface ofeach of the samples 2A-1 to 2A-3 were small. In particular, thevariations in Shift of the sample 2A-3 subjected to heat treatment at arelatively low temperature like the sample 2A, were similar to thevariations in Shift of each of the samples 2A-1 and 2A-2 whose heattreatment temperature was high.

Next, a change in electrical characteristics of the sample 2A by stresstests was measured.

FIG. 51A shows results of a positive gate BT (Bias-Temperature) stresstest. Note that the stress test described below was performed at asubstrate temperature of 150° C. In the positive gate BT stress test,first, I_(d)-V_(g) characteristics before the stress test were measured.In the measurement, the back gate voltage was 0 V, the drain voltage was0.1 V or 1.8 V, and the gate voltage was swept from −3.0 V to 3.0 V inincrements of 0.1 V. Next, I_(d)-V_(g) characteristics after the stresstest were measured. In the measurement, the drain voltage was 0 V, theback gate voltage was 0 V, and a gate voltage of 3.3 V was applied for 1hour. Note that measurement was performed 100 seconds, 300 seconds, 600seconds, 1000 seconds, 30 minutes, and 1 hour after stress application,and the value after 1 hour after the stress application is describedbelow. As shown in FIG. 51A, a change in Shift (ΔShift) before and afterthe positive gate BT stress test for 1 hour was as small as 0.19 V.

Positive gate BT stress tests were performed under the same conditions.The results measured 600 seconds, 1 hour, 5 hours, 12 hours after thestress application are shown in FIG. 78A; ΔShift measured after 12 hourswas 0.29 V, which was slightly larger than ΔShift measured after 1 hour.

FIG. 51B shows results of a negative gate BT stress test. Note that thestress test described below was performed at a substrate temperature of150° C. In the negative gate BT stress test, first, I_(d)-V_(g)characteristics before the stress test were measured. In themeasurement, the back gate voltage was 0 V, the drain voltage was 0.1 Vor 1.8 V, and the gate voltage was swept from −3.0 V to 3.0 V inincrements of 0.1 V. Next, I_(d)-V_(g) characteristics after the stresstest were measured. In the measurement, the drain voltage was 0 V, theback gate voltage was 0 V, and a gate voltage of −3.3 V was applied for1 hour. Note that measurement was performed 100 seconds, 300 seconds,600 seconds, 1000 seconds, 30 minutes, and 1 hour after stressapplication, and the value after 1 hour after the stress application isdescribed below. As shown in FIG. 51B, a change in ΔShift before andafter the negative gate BT stress test for 1 hour was as small as 0.13V.

Negative gate BT stress tests were performed under the same conditions,and the results measured 600 seconds, 1 hour, 5 hours, 12 hours afterthe stress application. The results are shown in FIG. 78B; ΔShiftmeasured after 12 hours was 0.15 V, which was almost the same as ΔShiftmeasured after 1 hour.

FIG. 51C shows results of a positive drain BT stress test. Note that thestress test described below was performed at a substrate temperature of150° C. In the positive drain BT stress test, first, I_(d)-V_(g)characteristics before the stress test were measured. In themeasurement, the back gate voltage was 0 V, the drain voltage was 0.1 Vor 1.8 V, and the gate voltage was swept from −3.0 V to 3.0 V inincrements of 0.1 V. Next, I_(d)-V_(g) characteristics after the stresstest were measured. In the measurement, the gate voltage was 0 V, theback gate voltage was 0 V, and a drain voltage of 1.8 V was applied for1 hour. Note that measurement was performed 100 seconds, 300 seconds,600 seconds, 1000 seconds, 30 minutes, and 1 hour after stressapplication, and the value after 1 hour after the stress application isdescribed below. As shown in FIG. 51C, a change in ΔShift before andafter the positive drain BT stress test for 1 hour was as small as 0.01V.

Positive drain BT stress tests were performed under the same conditions.The results measured 600 seconds, 1 hour, 5 hours, 12 hours after thestress application are shown in FIG. 78C; ΔShift measured after 12 hourswas −0.01 V, which was hardly changed from ΔShift measured after 1 hour.

FIG. 51D shows results of a negative back gate BT stress test. Note thatthe stress test described below was performed at a substrate temperatureof 150° C. In the negative back gate BT stress test, first, I_(d)-V_(g)characteristics before the stress test were measured. In themeasurement, the back gate voltage was −5 V, the drain voltage was 0.1 Vor 1.8 V, and the gate voltage was swept from −3.0 V to 3.0 V inincrements of 0.1 V. Next, I_(d)-V_(g) characteristics after the stresstest were measured. In the measurement, the drain voltage was 0 V, thegate voltage was 0 V, and a back gate voltage of −5 V was applied for 1hour. Note that measurement was performed 100 seconds, 300 seconds, 600seconds, 1000 seconds, 30 minutes, and 1 hour after stress application,and the value after 1 hour after the stress application is describedbelow. As shown in FIG. 51D, a change in ΔShift before and after thenegative back gate BT stress test for 1 hour was as small as 0.02 V.

Negative back gate BT stress tests were performed under the sameconditions. The results measured 600 seconds, 1 hour, 5 hours, 12 hoursafter the stress application are shown in FIG. 78D; ΔShift measuredafter 12 hours was 0.05 V, which was hardly changed from ΔShift measuredafter 1 hour.

Accordingly, the transistor in which the insulator 104 in contact withthe bottom surface of the oxide semiconductor was formed by a PECVDmethod using SiF₄ so that water, hydrogen, and the like in the insulator104 were reduced showed small changes in electrical characteristics whensubjected to stress tests. Thus, by employing the structure described inthis example, a highly reliable transistor can be provided.

The stacked film of the insulators 105, 103, and 104 in the sample 2Acorresponds to that of the sample 1A in Example 1, and the stacked filmof the insulators 105, 103, and 104 in the sample 2B corresponds to thatof the reference sample 1 in Example 1. By setting the number of watermolecules or hydrogen molecules (in particular, the number of watermolecules) released from the stacked film of the insulators 105, 103,and 104 within the range described in Example 1, the high reliability ofthe transistor can be obtained. Furthermore, although the heatingtemperature in the process for forming the transistor was approximately400° C., favorable transistor characteristics were able to be obtained.

Example 3

In this example, samples were formed in such a manner that a siliconoxide film was formed over a silicon substrate, and SiH₄ and SiF₄ wereintroduced to form a silicon oxide film containing fluorine thereover.The samples were analyzed by TDS and SIMS and the results will bedescribed. In this example, samples 3A-1 to 3A-8 were formed under theconditions that the flow rate of SiF₄ was fixed to 1.5 sccm and the flowrate of SiH₄ was changed; and samples 3B-1 to 3B-8 were formed under theconditions that the flow rate of SiF₄ was fixed to 10 sccm and the flowrate of SiH₄ was changed.

A method for forming the samples 3A-1 to 3A-8 and the samples 3B-1 to3B-8 is described. First, by thermal oxidation of a silicon wafer, a100-nm-thick silicon oxide film was formed on a surface of the siliconwafer. The thermal oxidation was performed at 950° C. in an oxygenatmosphere containing HCl at 3 volume % for 4 hours.

Then, a 300-nm-thick silicon oxide film containing fluorine was formedover the silicon oxide film by a PECVD method. The deposition conditionswere as follows: 1000 sccm of N₂O and 1000 sccm of Ar were used asdeposition gases; RF power source frequency was 60 MHz; RF power was 800W; deposition pressure was 133 Pa; and the substrate temperature was400° C. The flow rate of SiF₄ was 1.5 sccm for the samples 3A-1 to 3A-8,and was 10 sccm for the samples 3B-1 to 3B-8. The flow rate of SiH₄ was0 sccm for the samples 3A-1 and 3B-1, 0.2 sccm for the samples 3A-2 and3B-2, 1 sccm for the samples 3A-3 and 3B-3, 2 sccm for the samples 3A-4and 3B-4, 4 sccm for the samples 3A-5 and 3B-5, 8 sccm for the samples3A-6 and 3B-6, 10 sccm for the samples 3A-7 and 3B-7, and 20 sccm forthe samples 3A-8 and 3B-8.

FIG. 52 shows the calculated deposition rates of the silicon oxide filmscontaining fluorine of the samples 3A-1 to 3A-8 and the samples 3B-1 to3B-8 formed in the above manner. In FIG. 52 , the horizontal axisrepresents the flow rate [sccm] of SiH₄ for each sample, and thevertical axis represents the deposition rate [nm/min] of each sample.

As shown in FIG. 52 , in the samples 3A-1 to 3A-8 and the samples 3B-1to 3B-8, the deposition rate tends to be increased with an increase inthe flow rate of SiH₄. However, when the samples with the same flow rateof SiH₄ are compared, the deposition rates of the samples 3B-1 to 3B-8were slightly higher than those of the samples 3A-1 to 3A-8. Thedifference in deposition rate becomes larger with an increase in theflow rate of SiH₄.

The TDS analysis results of the samples 3A-1 to 3A-8 and the samples3B-1 to 3B-8 are shown in FIGS. 55A to 55H to FIGS. 58A to 58H. Notethat in the TDS analysis, the amount of a released gas with amass-to-charge ratio m/z=2, which corresponds to a hydrogen molecule andthe amount of a released gas with a mass-to-charge ratio m/z=18, whichcorresponds to a water molecule, were measured. FIGS. 55A to 55H showthe TDS measurement results of hydrogen in the samples 3A-1 to 3A-8, andFIGS. 56A to 56H show those of water in the samples 3A-1 to 3A-8. FIGS.57A to 57H show the TDS measurement results of hydrogen in the samples3B-1 to 3B-8, and FIGS. 58A to 58H show those of water in the samples3B-1 to 3B-8. In each of FIGS. 55A to 55H to FIGS. 58A to 58H, thehorizontal axis represents substrate heating temperature [° C.] and thevertical axis represents intensity proportional to the amount of areleased gas with a mass-to-charge ratio.

The number of hydrogen molecules released from each of the samples 3A-1to 3A-8 and the samples 3B-1 to 3B-8 was estimated from the measurementresults of hydrogen shown in FIGS. 55A to 55H and 57A to 57H. In FIG.53A, the horizontal axis represents the flow rate [sccm] of SiH₄ foreach sample, and the vertical axis represents the number of hydrogenmolecules [molecules/cm²] released from each sample. In FIG. 53B, thehorizontal axis represents the deposition rate [nm/min] of each sample,and the vertical axis represents the number of hydrogen molecules[molecules/cm²] released from each sample.

The number of water molecules released from each of the samples 3A-1 to3A-8 and the samples 3B-1 to 3B-8 was estimated from the measurementresults of water shown in FIGS. 56A to 56H and 58A to 58H. In FIG. 54A,the horizontal axis represents the flow rate [sccm] of SiH₄ for eachsample, and the vertical axis represents the number of water molecules[molecules/cm²] released from each sample. In FIG. 54B, the horizontalaxis represents the deposition rate [nm/min] of each sample, and thevertical axis represents the number of water molecules [molecules/cm²]released from each sample.

As shown in FIGS. 53A and 53B and FIGS. 54A and 54B, in the samples 3A-1to 3A-8 and the samples 3B-1 to 3B-8, the number of released hydrogenmolecules and the number of released water molecules tend to beincreased by an increase in the flow rate of SiH₄ or an increase indeposition rate. A significant difference between the samples 3A-1 to3A-8 and the samples 3B-1 to 3B-8 is not seen in FIGS. 53A and 53B andFIGS. 54A and 54B; accordingly, it seems that the difference in the flowrate of SiF₄ did not cause a significant difference.

As shown in FIGS. 55A to 55H and 57A to 57H, a large profile peak ofhydrogen is not seen in each of the samples 3A-1 to 3A-8 and the samples3B-1 to 3B-8 at any temperature, and the number of hydrogen moleculesreleased therefrom was significantly small.

As shown in FIGS. 56A to 56H and 58A to 58H, a large profile peak ofwater is seen in each of the samples 3A-1 to 3A-8 and the samples 3B-1to 3B-8 at a substrate temperature of approximately 100° C.;accordingly, which shows release of water. Furthermore, in the samples3A-1 to 3A-8 and the samples 3B-1 to 3B-8, as the flow rate of SiH₄increases, a peak in a high temperature region starts to rise at asubstrate temperature of approximately 400° C.

As shown in FIG. 54A, the number of water molecules released from eachof the samples 3B-1 to 3B-4 with a low flow rate of SiH₄ issignificantly large. The number of water molecules released from each ofthe samples 3B-1 to 3B-4 shown in FIGS. 58A to 58D shows a very sharppeak at a substrate temperature of approximately 100° C. In other words,a significant factor of the large number of water molecules releasedfrom each of the samples 3B-1 to 3B-4 is probably water moleculescorresponding to the peak at approximately 100° C. The water moleculescorresponding to this peak can be eliminated by heating the substrate ata substrate temperature of approximately 100° C.; thus, the number ofwater molecules released from each of the samples 3B-1 to 3B-4 can begreatly reduced by heating the substrate at approximately 100° C.

As described above, there is a trade-off between the deposition rate ofthe silicon oxide film containing fluorine, which depend on the flowrate of SiH₄, and the amounts of hydrogen and water in the film. Forexample, as shown in FIG. 52 and FIG. 54A, the flow rate of SiH₄ is setto greater than 1 sccm and less than 10 sccm, preferably, greater thanor equal to 2 sccm and less than or equal to 4 sccm, in which case theamounts of water and hydrogen in the insulator 104 and the depositionrate can be relatively favorable values. Note that it is preferable thatthe proportion of SiH₄ be determined as appropriate in view of theamounts of water and hydrogen in the silicon oxide film containingfluorine and the deposition rate.

Next, the samples 3A-1 to 3A-8 and the samples 3B-1 to 3B-8 weresubjected to SSDP-SIMS analysis to detect H, F, and N, and the resultsare shown in FIGS. 59A to 59C and FIGS. 60A to 60C. Note that each graphin FIGS. 59A to 59C and FIGS. 60A to 60C shows an average value of theconcentration of an element in a sample detected in a region 50 nm to100 nm above from an interface between the silicon oxide film and thesilicon oxide film containing fluorine. FIGS. 59A to 59C show theresults of the samples 3A-1 to 3A-8. FIG. 59A shows the detectionresults of H; FIG. 59B shows the detection results of F; and FIG. 59Cshows the detection results of N. FIGS. 60A to 60C show the results ofthe samples 3B-1 to 3B-8. FIG. 60A shows the detection results of H;FIG. 60B shows the detection results of F; and FIG. 60C shows thedetection results of N. In each of FIGS. 59A to 59C and FIGS. 60A to60C, the horizontal axis represents the flow rate [sccm] of SiH₄ foreach sample, and the vertical axis represents the average concentration[atoms/cm³] in the sample. Note that SIMS measurement was performed byusing an ADEPT-1010 quadrupole mass spectrometry instrument manufacturedby ULVAC-PHI, Inc.

As shown in FIG. 59A and FIG. 60A, the SIMS measurement also shows thatthe hydrogen concentration in each of the samples 3A-1 to 3A-8 and thesamples 3B-1 to 3B-8 tends to be increased with an increase in the flowrate of SiH₄. The hydrogen concentration in each of the samples 3A-1 to3A-8 and the samples 3B-1 to 3B-8 was within the range from 1×10²⁰atoms/cm³ to 1×10²¹ atoms/cm³, and a large increase was not observed.

As shown in FIG. 59B and FIG. 60B, the fluorine concentration in each ofthe samples 3A-1 to 3A-8 and the samples 3B-1 to 3B-8 tends to bedecreased with an increase in the flow rate of SiH₄. While the fluorineconcentration in each of the samples 3A-1 to 3A-8 was within the rangefrom 1×10²⁰ atoms/cm³ to 1×10²¹ atoms/cm³, the fluorine concentration ineach of the samples 3B-1 to 3B-8 was increased with an increase in theflow rate of SiF₄ and within the range from 1×10²¹ atoms/cm³ to 1×10²²atoms/cm³.

As shown in FIG. 59C and FIG. 60C, a clear tendency by an increase inthe flow rate of SiH₄ was not seen for the nitrogen concentration ineach of the samples 3A-1 to 3A-8 and the samples 3B-1 to 3B-8. When theflow rate of SiH₄ is low, the samples 3A-1 to 3A-8 and the samples 3B-1to 3B-8 have different tendencies; when the flow rate of SiH₄ is high,the concentrations of the samples 3A-1 to 3A-8 were substantially equalto those of the samples 3B-1 to 3B-8.

In this example, samples were formed by stacking a silicon oxide film, asilicon oxynitride film, a hafnium oxide film, a silicon oxide filmcontaining fluorine over a silicon substrate and evaluated by X-rayphotoelectron spectroscopy (XPS). For the XPS evaluation, samples 3C-1to 3C-4 were formed as reference samples. The outermost surface of thesample 3C-1 was silicon oxide deposited by a PECVD method. The outermostsurface of the sample 3C-2 was silicon oxide containing fluorinedeposited by a PECVD method. The outermost surface of the sample 3C-3was silicon oxide containing fluorine deposited by a PECVD method usinga deposition gas containing 0.2 sccm of SiH₄. The outermost surface ofthe sample 3C-4 was silicon oxide containing fluorine deposited by aPECVD method using a deposition gas containing 4 sccm of SiH₄.

A method for forming the samples used in the XPS analysis is described.First, by thermal oxidation of a silicon wafer, a 100-nm-thick siliconoxide film was formed on a surface of the silicon wafer. The thermaloxidation was performed at 950° C. in an oxygen atmosphere containingHCl at 3 volume % for 4 hours.

Then, a 10-nm-thick silicon oxynitride film was formed over the siliconoxide film by a PECVD method at a substrate temperature of 400° C.

Next, a 20-nm-thick hafnium oxide film was formed over the siliconoxynitride film by an ALD method. In the film formation by an ALDmethod, the substrate temperature was 200° C., and a source gas obtainedby vaporizing a solid containing tetrakis(dimethylamido)hafnium (TDMAH)and an O₃ gas) that was an oxidizer were used.

Then, a 30-nm-thick silicon oxide film containing fluorine was formedover the hafnium oxide film by a PECVD method. Note that for the sample3C-1 (comparative example), a silicon oxide film was formed by a PECVDmethod at a substrate temperature of 500° C.

For the samples 3C-2 to 3C-4, before the deposition of the silicon oxidefilm containing fluorine, pretreatment for letting SiH₄ flow at 200 sccmfor 20 seconds was performed. The deposition conditions were as follows:1.5 sccm of SiF₄, 1000 sccm of N₂O, and 1000 sccm of Ar were used asdeposition gases; RF power source frequency was 60 MHz; RF power was 800W; deposition pressure was 133 Pa; and the substrate temperature was400° C. In addition, 0.2 sccm of SiH₄ was added to the deposition gasesfor the sample 3C-3, and 4 sccm of SiH₄ was added to the depositiongases for the sample 3C-4.

The samples 3C-1 to 3C-4 formed in the above manner were analyzed by XPSand the results are shown in FIGS. 61A to 61C. FIG. 61A shows a spectrumcorresponding to the 2p orbital of Si; FIG. 61B shows a spectrumcorresponding to the is orbital of O; and FIG. 61C shows a spectrumcorresponding to the 1 s orbital of F. In each of FIGS. 61A to 61C, thehorizontal axis represents binding energy [eV] and the vertical axisrepresents the spectrum intensity. Table 2 shows the compositions[atomic %] of Si, O, C, and F in each of the samples 3C-1 to 3C-4.

TABLE 2 Si O C F Sample 3C-1 [atomic %] 29.0 61.9 9.0 — Sample 3C-2[atomic %] 29.1 59.1 8.5 3.3 Sample 3C-3 [atomic %] 29.1 59.3 8.0 3.6Sample 3C-4 [atomic %] 29.3 62.5 7.9 0.3

As shown in FIGS. 61A and 61B, a significant difference in the amountsof silicon and oxygen was not observed between the samples 3C-1 to 3C-4.However, when focusing on oxygen and fluorine, as the flow rate of SiH₄in the deposition gas is decreased and thus the flow rate of SiF₄ isrelatively increased, the proportion of fluorine is increased and theproportion of oxygen is decreased, as shown in Table 2.

As shown in FIG. 61C, each of the samples 3C-2 and 3C-3 with relativelyhigh flow rates of SiF₄ in the deposition gas shows a large peak of the1 s orbital of F. This peak appears in the region of a SiF covalent bond(higher than or equal to 685.4 eV and lower than or equal to 687.5 eV,the median value: 686.5 eV), which means that the SiF covalent bond isformed on a surface of each of the samples 3C-2 and 3C-3.

Example 4

In this example, samples in each of which a hafnium oxide film wasformed over a silicon substrate by an ALD method or an MOCVD method wereformed and analyzed by TDS, and the results will be described. In thisexample, three samples 4A to 4C were formed. Deposition for the sample4A was performed by an ALD method using two kinds of gases (O₃ and a gascontaining TDMAH); deposition for the sample 4B was performed by an ALDmethod using three kinds of gases (O₃, H₂O, and a gas containing TDMAH);and deposition for the sample 4C was performed by an MOCVD method.

Methods for forming the samples 4A to 4C are described.

For the sample 4A, a 20-nm-thick hafnium oxide film was formed over thesilicon substrate by an ALD method. In the film formation by an ALDmethod, the substrate temperature was 200° C., and a source gas obtainedby vaporizing a solid containing TDMAH and an O₃ gas) that was anoxidizer were used. FIG. 62A is a timing diagram of deposition gases forthe sample 4A.

As shown in FIG. 62A, in the deposition for the sample 4A, first,purging of a chamber was performed with O₃. As the O₃ purging,introduction of O₃ for 0.025 seconds was repeated 20 times. Next, asource gas obtained by vaporizing a solid containing TDMAH wasintroduced for 0.5 seconds, N₂ purging was performed for 45 seconds, O₃was introduced for 0.1 seconds, and N₂ purging was performed for 25seconds. Then, the introduction of TDMAH, the N₂ purging, theintroduction of O₃, and the N₂ purging were regarded as one cycle, andthis cycle was repeated until the thickness reached 20 nm.

In the deposition for the sample 4B, a 20-nm-thick hafnium oxide filmwas formed over a silicon substrate by an ALD method. The deposition byan ALD method was performed at a substrate temperature of 200° C. usingthree kinds of deposition gases: a gas obtained by vaporizing a solidcontaining TDMAH as a source and O₃ and H₂O as oxidizers. FIG. 62B is atiming diagram of deposition gases for the sample 4B.

As shown in FIG. 62B, in the deposition for the sample 4B, the sourcegas obtained by vaporizing a solid containing TDMAH was introduced for0.5 seconds, N₂ purging was performed for 45 seconds, H₂O was introducedfor 0.03 seconds, and N₂ purging was performed for 5 seconds. Then, O₃was introduced for 0.1 seconds and N₂ purging was performed for 5seconds. This sequence of the introduction of O₃ and the N₂ purging wasperformed 10 times. After that, the introduction of TDMAH, the N₂purging, the introduction of H₂O, the N₂ purging, and 10 times of thesequence of the introduction of 03 and the N₂ purging were regarded asone cycle, and this cycle was repeated until the thickness reached 20nm.

In the deposition for the sample 4C, a 20-nm-thick hafnium oxide filmwas formed over a silicon substrate by an MOCVD method. In thedeposition for the sample 4C, a solution obtained by dissolvingtetrakis(ethylmethylamino)hafnium (TEMAH) in ethylcyclohexane (ECH) at aconcentration of 0.1 mol/l was supplied to a vaporizing chamber at aflow rate of 0.1 sccm, and a gas containing TEMAH was introduced fromthe vaporizing chamber to a chamber. The other deposition conditionswere as follows: 1000 sccm of O₂, 1800 sccm of Ar, and 1080 sccm of N₂were used as the other deposition gases, the deposition pressure was1000 Pa, and the substrate temperature was 400° C.

The samples 4A to 4C formed in the above manner were analyzed by TDS andthe results are shown in FIG. 63A. Note that in the TDS analysis, theamount of a released gas with a mass-to-charge ratio water moleculem/z=18, which corresponds to a water molecule, was measured. In FIG.63A, the horizontal axis represents substrate heating temperature [° C.]and the vertical axis represents intensity proportional to the amount ofa released gas with a mass-to-charge ratio.

FIG. 63B shows the numbers of water molecules released from the samples4A to 4C, which were calculated from the profiles shown in FIG. 63A. InFIG. 63B, the horizontal axis represents the samples and the verticalaxis represents the numbers of water molecules [molecules/cm²] releasedfrom the samples.

FIGS. 63A and 63B indicate that the number of water molecules releasedfrom each of the samples 4B and 4C can be approximately a fourth of thenumber of water molecules released from the sample 4A. The number ofwater molecules released from the sample 4A was 1.1×10¹⁶ molecules/cm²,that from the sample 4B was 2.8×10¹⁵ molecules/cm², and that from thesample 4C was 2.5×10¹⁵ molecules/cm². Thus, as described in the aboveembodiment, the number of water molecules released from each of thesamples 4B and 4C measured by TDS satisfied a range greater than orequal to 1.0×10¹³ molecules/cm² and less than or equal to 1.0×10¹⁶molecules/cm², and also satisfied a range greater than or equal to1.0×10¹³ molecules/cm² and less than or equal to 3.0×10¹⁵ molecules/cm².

In the formation of the sample 4B, the introduction of O₃ serving as anoxidizer and the N₂ purging are repeated multiple times in a short time,whereby excess hydrogen atoms and the like can be more certainly removedfrom TEMAH adsorbed onto the substrate surface and eliminated from thechamber. It is inferable that in the case where two kinds of oxidizers(O₃ and H₂O) are introduced, more excess hydrogen atoms and the like canbe removed from TEMAH adsorbed onto the substrate surface. In thismanner, hydrogen atoms are prevented from entering the insulator and thelike during the deposition, so that the amounts of water, hydrogen, andthe like in the hafnium oxide film can be small.

The deposition for the sample 4C can be performed at a high temperature(e.g., 200° C. or higher) relatively easily as compared with thedeposition for the sample 4A performed within the temperature range ofthe ALD window; therefore, it is inferable that hydrogen and water inthe film can be readily reduced in the sample 4C.

As described above, a hafnium oxide film in which hydrogen and water arereduced can be formed by an ALD method or an MOCVD method.

Example 5

In this example, the relationship between conditions for the depositionof the silicon nitride film and the numbers of hydrogen molecules andwater molecules released from the silicon nitride film was examined byTDS analysis.

<Flow of Deposition>

A flow of deposition of the silicon nitride film is described. A PECVDmethod was employed for the deposition.

First, preparation for deposition was performed. The preparationconsists of Step S001 and Step S002. Chamber cleaning was performed atStep S001. For example, a film deposited on an inner wall of a chambercan be removed by the cleaning. An NF₃ gas was used as a cleaning gas,and an RF power source was used for application of voltage. Then, atStep S002, a 0.89-μm-thick film was formed as pre-coating.

Next, deposition of samples was performed. The deposition of samplesconsists of Steps S101 to S106. Steps S101 to S106 will be describedlater. Deposition of a plurality of samples was sequentially performed(e.g., a first sample was deposited, a second sample was deposited, andthen a third sample was deposited), and Step S001 and Step S002 wereperformed again when the cumulative deposition thickness reached apredetermined value (here, 20 μm).

The deposition of samples is described in details. Steps S101 to S106were performed for the deposition of samples. The substrate temperaturewas 400° C. during Steps S101 to S106.

At Step S101, the RF power source was turned off, an auto pressurecontroller (APC) was turned off, the distance between electrodes was 17mm, silane was used as a gas, and treatment for letting the gas flow wasperformed for two minutes. The flow rate of silane was 800 sccm. StepS101 is referred to as silane flush in some cases.

At Step S102, the RF power source was turned off, the pressure, thedistance between electrodes, and the flow rate of a gas were set to thesame as those at Step S103, and treatment for letting the gas flow wasperformed for 20 seconds to stabilize the flow rate of a gas and thepressure.

At Step S103, the RF power, the pressure, the distance betweenelectrodes, and the flow rate of a gas were set to the conditions to bedescribed later, and a silicon nitride film was formed. The treatmenttime for Step S103 can be determined in accordance with a desiredthickness.

At Step S104, the RF power source was turned off, the pressure was 133Pa, the distance between electrodes was 15 mm, nitrogen was used as agas, and treatment for letting the gas flow was performed for 15seconds. The flow rate of nitrogen was 2000 sccm.

At Step S105, the RF power source was 10 W, the pressure was 133 Pa, thedistance between electrodes was 15 mm, nitrogen was used as a gas, andtreatment for letting the gas flow was performed for one minute. Theflow rate of nitrogen was 2000 sccm.

At Step S106, the RF power source was turned off, the pressure was 133Pa, the distance between electrodes was 65 mm, the substrate was movedto a substrate transfer position, argon was used as a gas, and treatmentfor letting the gas flow was performed for 20 seconds. The flow rate ofargon was 250 sccm.

<Formation of Samples>

Next, the relationship between the deposition flow and the numbers ofhydrogen molecules and water molecules released from the silicon nitridefilm formed by a PECVD method was examined.

First, a p-type silicon wafer with a size of 126.6 mm square and athickness of 0.7 mm was prepared. Next, the silicon wafer was thermallyoxidized to form a 100-nm-thick silicon oxide film. Then, the wafer wasdivided into four samples each having a size of 35 mm square (samplesA01 to A04).

Then, a 100-nm-thick silicon nitride film was formed over the siliconoxide film by a PECVD method.

Each of the samples A01 and A02 was subjected to Steps S101 to S106described above to form a silicon nitride film (with S101/S104/S105).

Each of the samples A03 and A04 was subjected to Steps S102, S103, andS106 in this order to form a silicon nitride film (w/o S101/S104/S105).

At Step S103, the RF power was 900 W, the pressure was 40 Pa, thedistance between electrodes was 17 mm, and silane, nitrogen, and ammoniawere used as a gas. The flow rates of silane, nitrogen, and ammonia were20 sccm, 500 sccm, and 10 sccm, respectively.

Note that the cumulative deposition in the chamber just before theformation of the samples A01 and A03 was approximately 0.9 μm. Thecumulative deposition in the chamber just before the formation of thesamples A02 and A04 was approximately 2.8 μm.

<TDS Analysis>

The samples A01 to A04 were subjected to TDS measurement. Note that eachof the samples A01 to A04 was divided into 1 cm squares for the TDSmeasurement.

FIGS. 64A and 64B show the TDS analysis results of the samples A01 andA03. FIG. 64A shows the result with a mass-to-charge ratio m/z=2 (e.g.,H2). FIG. 64B shows the result with m/z=18 (e.g., H₂O). FIGS. 65A and65B each show the numbers of molecules released from the samples A01 toA04 calculated by summations of TDS analysis results in the allmeasurement temperature range. In FIGS. 65A and 65B, it is assumed thatall the results with m/z=2 are derived from hydrogen and all the resultswith m/z=18 are derived from water.

The results of FIGS. 64A and 64B and FIGS. 65A and 65B show that thenumber of hydrogen molecules released from the samples A01 and A02subjected to Steps S101, S104, and S105 is small. The number of hydrogenmolecules released from each of the samples A01 and A02 was less than orequal to 2.0×10¹⁵ molecules/cm². Step S101 (silane flush) probablycontributes to suppressed hydrogen release.

The number of released hydrogen molecules even in the samples which werenot subjected to Steps S101, S104, and S105 decreases as the cumulativedeposition increases, and the number of hydrogen molecules released fromthe sample A04 was 9.0×10¹⁵ molecules/cm².

Example 6

In this example, the numbers of hydrogen molecules and water moleculesreleased from the silicon nitride film were examined by TDS analysis.

<Formation of Samples>

A method for forming samples is described below. First, two p-typesilicon wafers each having a size of 126.6 mm square were prepared.Next, each of the silicon wafers was thermally oxidized to form a100-nm-thick silicon oxide film. The two silicon wafers each includingthe oxide film were individually divided, and 17 samples each having asize of 35 nm square were obtained from the two wafers. The obtained 17samples each having a size of 35 nm square are referred to as samplesB01 to B17.

A 100-nm-thick silicon nitride film was formed over the silicon oxidefilm of each of the samples B01 to B17 by a PECVD method. Steps S101 toS106 described in Example 5 were employed for the deposition.

The conditions of Step S103 performed on the samples B01 to B17 aredescribed below. The substrate temperature was 400° C. The RF powersource frequency was 27 MHz. The distance between electrodes was 17 mm.The flow rate of nitrogen was 500 sccm. The flow rate of silane was A[sccm], that of ammonia was B [sccm], the RF power was C [W], thepressure in the deposition was D [Pa]. The values of A to D used for thedeposition of the samples B01 to B17 are described below.

The conditions for the sample B01 were as follows: the power C was 900W; the pressure D was 40 Pa; the flow rate B of ammonia was 10 sccm; andthe flow rate A of silane was 20 sccm.

The conditions for the samples B02 to B05 were the same as those for thesample B01 except for the flow rate A of silane. The conditions for thesamples B02 to B05 are described. The flow rate A of silane for sampleB02 was 12 sccm; for the sample B03, 16 sccm; for the sample B04, 24sccm; and for the sample B05, 28 sccm. The power C was 900 W; thepressure D was 40 Pa; and the flow rate B of ammonia was 10 sccm.

The conditions for the samples B06 to B09 were the same as those for thesample B01 except for the flow rate B of ammonia. The conditions for thesamples B06 to B09 are described. The flow rate B of ammonia for thesample B06 was 0 sccm; for the sample B07, 20 sccm; for the sample B08,30 sccm; and for the sample B09, 40 sccm. The power C was 900 W; thepressure D was 40 Pa; and the flow rate A of silane was 20 sccm.

The conditions for the samples B10 to B13 were the same as those for thesample B01 except for the power C. The conditions for the samples B10 toB13 are described. The power C for the sample B10 was 600 W; for thesample B11, 700 W; for the sample B12, 800 W; and for the sample B13,1000 W. The pressure D was 40 Pa; the flow rate A of silane was 20 sccm;and the flow rate B of ammonia was 10 sccm.

The conditions for the samples B14 to B17 were the same as those for thesample B01 except for the pressure D. The conditions for the samples B14to B17 are described. The pressure D for the sample B14 was 30 Pa; forthe sample B15, 50 Pa; for the sample B16, 100 Pa; and for the sampleB17, 150 Pa. The power C was 900 W; the flow rate A of silane was 20sccm; and the flow rate B of ammonia was 10 sccm.

Through the above steps, the samples B01 to B17 each including a siliconnitride film were obtained.

<TDS Analysis>

The samples B01 to B17 were subjected to TDS measurement. Note that eachof the samples B01 to B17 was divided into 1 cm squares for the TDSmeasurement.

FIGS. 66A and 66B show the TDS analysis results of the samples B01 toB05 with different flow rates of silane. FIG. 66A shows the result witha mass-to-charge ratio m/z=2 (e.g., H₂). FIG. 66B shows the result withm/z=18 (e.g., H₂O). The numbers in the graphs indicate the flow rates ofsilane.

FIGS. 67A and 67B show the TDS analysis results of the samples B01 andB06 to B09 with different flow rates of ammonia. FIG. 67A shows theresult with a mass-to-charge ratio m/z=2 (e.g., H2). FIG. 67B shows theresult with m/z=18 (e.g., H₂O). The numbers in the graphs indicate theflow rates of ammonia.

FIGS. 68A and 68B show the TDS analysis results of the samples B01 andB10 to B13 with different RF power source. FIG. 68A shows the resultwith a mass-to-charge ratio m/z=2 (e.g., H₂). FIG. 68B shows the resultwith m/z=18 (e.g., H₂O). The numbers in the graphs indicate the powersource values.

FIGS. 69A and 69B show the TDS analysis results of the samples B01 andB14 to B17 with different deposition pressures. FIG. 69A shows theresult with a mass-to-charge ratio m/z=2 (e.g., H2). FIG. 69B shows theresult with m/z=18 (e.g., H₂O). The numbers in the graphs indicate thepressure values.

FIG. 70A, FIG. 71A, FIG. 72A, and FIG. 73A show the numbers of releasedmolecules calculated by summations of TDS analysis results in the allmeasurement temperature range of FIG. 66A, FIG. 67A, FIG. 68A, and FIG.69A. The horizontal axes in FIG. 70A, FIG. 71A, FIG. 72A, and FIG. 73Arepresent the flow rate of silane, the flow rate of ammonia, thepressure, and the power, respectively. Here, it is assumed that all theresults with m/z=2 are derived from hydrogen.

FIG. 70B, FIG. 71B, FIG. 72B, and FIG. 73B show the numbers of releasedmolecules calculated by summations of TDS analysis results in the allmeasurement temperature range of FIG. 66B, FIG. 67B, FIG. 68B, and FIG.69B. The horizontal axes in FIG. 70B, FIG. 71B, FIG. 72B, and FIG. 73Brepresent the flow rate of silane, the flow rate of ammonia, thepressure, and the power, respectively. Here, it is assumed that all theresults with m/z=18 are derived from water.

[Results with m/z=2]

First, the results with m/z=2 are described. According to FIG. 66A andFIG. 70A, when the flow rate of silane is higher than or equal to 16sccm, a temperature at which release of hydrogen molecules starts tendsto be higher and the number of released hydrogen molecules tends to besmaller than when the flow rate of silane is 12 sccm. According to FIG.67A and FIG. 71A, the number of released hydrogen molecules stronglydepends on the flow rate of ammonia; the number of released hydrogenmolecules is the smallest when the flow rate of ammonia is 0 sccm andtends to be increased with an increase in the flow rate of ammonia. Thenumber of released hydrogen molecules at a flow rate of ammonia of 0sccm is 1.3×10¹⁵ molecules/cm². According to FIG. 68A, FIG. 69A, FIG.72A, and FIG. 73A, the dependence of the number of released hydrogenmolecules on the RF power and that on the deposition pressure are small.Therefore, the temperature at which hydrogen release starts can beincreased by setting the flow rate of silane for the deposition ofsilicon nitride to be 16 sccm or higher. Moreover, the hydrogen releasecan be suppressed by setting the flow rate of ammonia to be low.

[Results with m/z=18]

Next, the results with m/z=18 are described. According to FIG. 66B, whenthe flow rate of silane is 28 sccm, the number of released watermolecules is slightly increased at approximately 300° C. According toFIG. 67B, when the flow rate of ammonia is 40 sccm, the number ofreleased water molecules is slightly increased at approximately 300° C.According to FIG. 68B, when the power is 700 W, the number of releasedwater molecules is significantly increased at approximately 300° C.; andwhen the power is 800 W or higher, the number of released watermolecules is reduced. Therefore, when the power is 800 W or higher, therelease of water can probably be suppressed. According to FIG. 72B, whenthe power is 800 W, the total number of released water molecules can beas low as 4.2×10¹⁴ molecules/cm².

Example 7

In this example, a sample 7A in which a silicon nitride film was formedover a silicon substrate and a sample 7B in which a silicon oxide filmwas formed over a silicon substrate were formed and analyzed by TDS, andthe results are described.

A method for forming the samples used in the TDS analysis is described.For the sample 7A, a 50-nm-thick silicon nitride film was formed over asilicon wafer by a PECVD method. The deposition conditions were asfollows: 20 sccm of SiH₄, 10 sccm of NH₃, and 500 sccm of N₂ were usedas deposition gases; RF power source frequency was 27 MHz; RF power was900 W; deposition pressure was 40 Pa; and the substrate temperature was400° C.

For the sample 7B, silicon oxide was deposited to a thickness of 50 nmover the silicon wafer by a PECVD method. The deposition conditions wereas follows: 15 sccm of tetraethoxysilane (TEOS) (chemical formula:Si(OC₂H₅)₄) and 750 sccm of O₂ were used as deposition gases; the RFpower source frequency was 27 MHz; the RF power was 300 W; thedeposition pressure was 100 Pa; and the substrate temperature was 400°C.

The samples 7A and 7B formed in the above manner were subjected to TDSanalysis and the results are shown in FIGS. 79A and 79B and FIGS. 80Aand 80B. Note that in the TDS analysis, the amount of a released gaswith a mass-to-charge ratio m/z=2, which corresponds to a hydrogenmolecule and the amount of a released gas with a mass-to-charge ratiom/z=18, which corresponds to a water molecule, were measured. FIG. 79Aand FIG. 80A show the measurement results of hydrogen, and FIG. 79B andFIG. 80B show the measurement results of water. In each of FIGS. 79A and79B and FIGS. 80A and 80B, the horizontal axis represents substrateheating temperature [° C.] and the vertical axis represents intensityproportional to the amount of a released gas with a mass-to-chargeratio.

The numbers of hydrogen molecules and water molecules released from thesample 7A and sample 7B were calculated from the profiles shown in FIGS.79A and 79B and FIGS. 80A and 80B. As the results, the number ofhydrogen molecules released from the sample 7A was 1.7×10¹⁵molecules/cm², and the number of water molecules released from thesample 7A was 6.3×10¹⁴ molecules/cm². The number of hydrogen moleculesreleased from the sample 7B was 1.3×10¹⁵ molecules/cm², and the numberof water molecules released from the sample 7B was 2.1×10¹⁵molecules/cm². Thus, the number of hydrogen molecules and the number ofwater molecules contained in the samples 7A and 7B were relativelysmall.

As shown in FIG. 79A and FIGS. 80A and 80B, a large peak was notobserved in the profiles of hydrogen molecules and water molecules in asubstrate temperature range of lower than or equal to 400° C. In FIG.79B, although peaks were observed in the profile of water molecules in asubstrate temperature range of lower than or equal to 400° C., the peakintensity was low as a whole. For this reason, the numbers of hydrogenmolecules and water molecules released from the silicon nitride film andthe silicon oxide film described in this example are probably small whenthe substrate heating temperature for the formation of the insulator 104described in the above embodiment (for example, higher than or equal to350° C. and lower than or equal to 445° C.) is employed. Consequently,even when the silicon nitride film and the silicon oxide film describedin this example are provided below the insulator 104 described in theabove embodiment, the silicon nitride film and the silicon oxide filmhardly supply impurities such as hydrogen or water to the oxidesemiconductor at the time of heat treatment in or after the formation ofthe insulator 104.

Accordingly, for example, the silicon nitride film of the sample 7A canbe provided in the insulator 1581 a and the like illustrated in FIG. 33and FIG. 34 in the above embodiment as a film for preventing hydrogendiffusion. Furthermore, for example, the silicon oxide film of thesample 7B can be provided in the insulator 1584 and the like illustratedin FIG. 33 and FIG. 34 in the above embodiment as an interlayerinsulating film.

Example 8

In this example, samples in each of which In—Ga—Zn oxide was depositedover a silicon substrate, the oxide was partly etched, and then heattreatment was performed were formed and analyzed by SIMS and hard X-rayphotoelectron spectroscopy (HX-PES), and the results are described.

First, a method for forming the samples used for the SIMS analysis isdescribed. For the SIMS analysis, eight samples 8A to 8H were formed.

First, In—Ga—Zn oxide was deposited over a silicon wafer to a thicknessof 100 nm by a DC sputtering method. Note that the In—Ga—Zn oxide wasdeposited using a target in which In:Ga:Zn=1:1:1 [atomic ratio], andthis oxide is referred to as an In—Ga—Zn oxide (111) in some cases. Asdeposition gases, an argon gas at 30 sccm and an oxygen gas at 15 sccmwere used.A As deposition gases, 30 sccm of an argon gas and 15 sccm ofan oxygen gas were used. A deposition pressure was 0.7 Pa (measured byMiniature Gauge MG-2 manufactured by CANON ANELVA CORPORATION). Adeposition power was 500 W. A substrate temperature was 300° C. Adistance between the target and the substrate was 60 mm.

Next, the samples 8B to 8H were subjected to heat treatment at 450° C.in a nitrogen atmosphere for an hour and further subjected to heattreatment at 450° C. in an oxygen atmosphere for an hour.

Next, in each of the samples 8B to 8H, the thickness of In—Ga—Zn oxide(111) was reduced by an ICP dry etching method by approximately 20 nm.The ICP dry etching of the In—Ga—Zn oxide (111) consists of three steps.The treatment conditions for the first step were as follows: thepressure was 1.2 Pa; the RF power was 1000 W on the upper side and 400 Won the lower side; etching gases were 20 sccm of methane and 80 sccm ofargon; and the treatment time was 53 seconds. The treatment conditionsfor the second step were as follows: the pressure was 5.2 Pa; the RFpower was 500 W on the upper side and 50 W on the lower side; theetching gas was 200 sccm of oxygen; and the treatment time was 3seconds. The treatment conditions for the third step were as follows:the pressure was 2.6 Pa; the RF power was 500 W on the upper side and 50W on the lower side; the etching gas was 200 sccm of oxygen; and thetreatment time was 60 seconds.

Next, the samples 8C to 8E were subjected to heat treatment in anitrogen atmosphere for an hour, and the samples 8F to 8H were subjectedto heat treatment in an oxygen atmosphere for an hour. The heattreatment temperature for the samples 8C and 8F was 300° C., that forthe samples 8D and 8G was 350° C., and that for the samples 8E and 8Hwas 400° C.

That is, the sample 8A is a sample in which the process up to thedeposition of the In—Ga—Zn oxide (111) is finished; the sample 8B is asample in which the process up to the etching of the In—Ga—Zn oxide(111) is finished; the samples 8C to 8E are samples subjected to theheat treatment in a nitrogen atmosphere after the etching; and thesamples 8F to 8H are samples subjected to the heat treatment in anoxygen atmosphere after the etching.

The SIMS analysis results of the samples 8A to 8H formed in this mannerare shown in FIGS. 81A and 81B. FIG. 81A is a graph showing the resultsof the samples 8A to 8E, and FIG. 81B is a graph showing the results ofthe samples 8A, 8B, and 8F to 8H. In each of FIGS. 81A and 81B, thehorizontal axis represents the depth [nm] (a depth from a surface of theIn—Ga—Zn oxide (111)), and the vertical axis represents the hydrogenconcentration [atoms/cm³]. Note that the SIMS analysis was performedfrom the surface of the In—Ga—Zn oxide (111) (the depth: 0 nm) towardthe silicon wafer, and the quantitative range was from the surface ofthe In—Ga—Zn oxide (111) to a depth of 60 nm. Note that SIMS measurementwas performed by using an ADEPT-1010 quadrupole mass spectrometryinstrument manufactured by ULVAC-PHI, Inc.

As shown in FIGS. 81A and 81B, the hydrogen concentration in the sample8A is very close to the background value. In contrast, the hydrogenconcentration in the sample 8B is approximately 1×10²² atoms/cm³ in thevicinity of the surface of the In—Ga—Zn oxide (111), and is similar tothat of the sample 8A in a region 50 nm deep or more from the surface.Thus, in the sample 8B, hydrogen is diffused to a region from thesurface to a depth of 50 nm. The hydrogen is probably derived frommethane in an etching gas used for forming the sample 8B.

As shown in FIG. 81A, as compared with the hydrogen concentration in thesample 8B, the hydrogen concentration in each of the samples 8C to 8E islow at least in a region from the surface of the In—Ga—Zn oxide (111) toa depth of approximately 30 nm. This indicates that hydrogen diffused inthe In—Ga—Zn oxide (111) by the etching is released by the heattreatment in a nitrogen atmosphere.

The hydrogen concentration in the sample 8C subjected to heat treatmentat 300° C. is approximately 1×10²⁰ atoms/cm³, and the hydrogenconcentration in the sample 8D subjected to heat treatment at 350° C. isapproximately 1.2×10¹⁹ atoms/cm³. In contrast, the hydrogenconcentration in the sample 8E subjected to heat treatment at 400° C. issimilar to that in the sample 8A. This is probably because the heatingtemperatures for the samples 8C and 8D are low, so that trap of hydrogenand release of hydrogen occur in balance in oxygen vacancy sites in theIn—Ga—Zn oxide (111) and thus, the hydrogen concentration therein is inequilibrium. Furthermore, during the heat treatment in a nitrogenatmosphere, oxygen is released, that is, oxygen vacancies are increased,which increases the number of hydrogen atoms trapped in oxygen vacancysites.

As shown in FIG. 81B, as compared with the hydrogen concentration in thesample 8B, the hydrogen concentration in each of the samples 8F to 8H islow at least in a region from the surface of the In—Ga—Zn oxide (111) toa depth of approximately 40 nm. This indicates that hydrogen diffused inthe In—Ga—Zn oxide (111) by the etching is released by the heattreatment in an oxygen atmosphere.

The hydrogen concentration in the sample 8F subjected to heat treatmentat 300° C. is approximately 1.1×10¹⁹ atoms/cm³. In contrast, thehydrogen concentration in each of the sample 8G subjected to heattreatment at 350° C. and the sample 8H subjected to heat treatment at400° C. is similar to that in the sample 8A. This is probably becausethe heating temperature for the sample 8F is low, so that trap ofhydrogen and release of hydrogen occur in balance in oxygen vacancysites in the In—Ga—Zn oxide (111) and thus, the hydrogen concentrationtherein is in equilibrium.

The hydrogen concentration in each of the samples 8F to 8H heated in anoxygen atmosphere can be reduced at a low heat treatment temperature ascompared with the samples 8C to 8E heated in a nitrogen atmosphere. Thisis probably because in each of the samples 8F to 8H, oxygen vacanciescan be reduced by being filled with oxygen supplied by the heattreatment in an oxygen atmosphere, which can reduce the number ofhydrogen atoms trapped in oxygen vacancy sites.

Next, the results of HX-PES analysis are described. For the HX-PESanalysis, three samples were used: a sample 8I formed in a mannersimilar to that of the sample 8A; a sample 8J formed in a manner similarto that of the sample 8B; and a sample 8K formed in a manner similar tothat of the sample 8G.

FIG. 82 shows the HX-PES analysis results of the samples 8I to 8K. InFIG. 82 , the horizontal axis represents binding energy [eV] and thevertical axis represents the intensity of a signal (arbitrary unit).Note that the data in FIG. 82 is quantified on the basis of the Fermilevel of Au, and 0 eV on the horizontal axis is energy close to theFermi level of the In—Ga—Zn oxide (111). In addition, a region from 0 eVto 3.2 eV on the horizontal axis corresponds to an energy gap of theIn—Ga—Zn oxide (111).

According to FIG. 82 , the signal intensity of the sample 8J is higherthan that of the sample 8I in the region from 0 eV to 3.2 eV. Thespectrum of the sample 8J has a peak at around 2.8 eV and a peak in aregion from 0 eV to 0.5 eV. Since the region from 0 eV to 3.2 eVcorresponds to the energy gap of the In—Ga—Zn oxide (111) as describedabove, it can be found that the sample 8J having a peak at around 2.8 eVand a peak in the region from 0 eV to 0.5 eV includes defect stateswithin the energy gap. Note that the peak position might be changeddepending on the method for analyzing the graph, for example.

The peak at around 2.8 eV of the sample 8J is positioned at a deep levelof the energy gap, and presumably derived from defect statescorresponding to oxygen vacancies in the In—Ga—Zn oxide (111). The peakin the region from 0 eV to 0.5 eV of the sample 8J is positioned at ashallow level of the energy gap, and presumably derived from defectstates corresponding to hydrogen trapped in oxygen vacancies in theIn—Ga—Zn oxide (111). Therefore, it is found that the In—Ga—Zn oxide(111) subjected to the aforementioned etching includes oxygen vacanciesand hydrogen atoms trapped in the oxygen vacancies.

In contrast, the sample 8K subjected to the etching and then heattreatment in an oxygen atmosphere has a spectrum substantially the samein shape as that of the sample 8I, and unlike the sample 8J, the signalintensity of the sample 8K at around 2.8 eV and in the region from 0 eVto 0.5 eV is significantly low. However, a small peak appears at around2.8 eV also in the spectrum of the sample 8K, and the signal intensityat around 2.8 eV is slightly higher than that of the sample 8I. Thisshows that oxygen vacancies formed in the In—Ga—Zn oxide (111) by theetching and hydrogen trapped in oxygen vacancies can be reduced by heattreatment.

Consequently, in the above embodiment, hydrogen diffused in thesemiconductor 106 b can be released by heat treatment performed afterthe formation of the semiconductor 106 b having a pattern. Therefore,defect states caused by diffusion of hydrogen and the like into thesemiconductor 106 b can be reduced. The use of such an oxidesemiconductor with a reduced density of defect states makes it possibleto provide a transistor with stable electrical characteristics.

Example 9

In this example, a sample 9A and a sample 9B were formed as transistorseach having an electron trap region in the insulator 103. The thresholdvoltages of the transistors, which were changed by injection ofelectrons into the insulator 103, were measured.

FIGS. 9A and 9B and other drawings can be referred to for the structureof the transistor, and FIGS. 13A to 13H, FIGS. 14A to 14F, and FIGS. 15Ato 15D and other drawings can be referred to for the method forfabricating the transistor.

First, a silicon substrate in which a 100-nm-thick silicon oxide film, a280-nm-thick silicon nitride oxide film, a 300-nm-thick silicon oxidefilm, and a 300-nm-thick silicon oxide film were stacked in this orderwas prepared as the substrate 100.

Next, a 35-nm-thick aluminum oxide film was formed as the insulator 101by a sputtering method.

Then, a 150-nm-thick silicon oxide film was formed by a PECVD method. Aresist was formed over the silicon oxide film and processing wasperformed using the resist, whereby the insulator 107 was formed.

Next, titanium nitride was deposited to a thickness of 5 nm and tungstenwas deposited thereover to a thickness of 250 nm by a CVD method. Then,CMP treatment was performed to form the conductor 102 embedded in theinsulator 107.

Then, a 10-nm-thick silicon oxide film was formed as the insulator 105by a PECVD method. The deposition conditions were as follows: 1 sccm ofSiH₄ and 800 sccm of N₂O were used as deposition gases; RF power sourcefrequency was 60 MHz; RF power was 150 W; deposition pressure was 40 Pa;and the substrate temperature was 500° C.

Next, a 20-nm-thick hafnium oxide film was formed as the insulator 103by an ALD method. In the film formation by an ALD method, the substratetemperature was 200° C., and a gas obtained by vaporizing a solidcontaining tetrakis(dimethylamido)hafnium (TDMAH) was used as a sourcegas and an O₃ gas) was used as an oxidizer.

Then, a 30-nm-thick silicon oxide film was formed as the insulator 104by a PECVD method. The deposition conditions were as follows: 1 sccm ofSiH₄ and 800 sccm of N₂O were used as deposition gases; RF power sourcefrequency was 60 MHz; RF power was 150 W; deposition pressure was 40 Pa;and the substrate temperature was 500° C.

Next, heat treatment was performed at 490° C. in an oxygen atmospherefor an hour.

Next, a 20-nm-thick In—Ga—Zn oxide film was formed by a DC sputteringmethod to form an oxide to be the insulator 106 a using a target havingan atomic ratio of In:Ga:Zn=1:3:4 and deposition gases of an argon gasat 40 sccm and an oxygen gas at 5 sccm. A deposition pressure was 0.7 Pa(measured by Miniature Gauge MG-2 manufactured by CANON ANELVACORPORATION). A deposition power was 500 W. A substrate temperature was200° C. A distance between the target and the substrate was 60 mm.

Next, a 15-nm-thick In—Ga—Zn oxide film was formed by a DC sputteringmethod to form an oxide to be the semiconductor 106 b using a targethaving an atomic ratio of In:Ga:Zn=1:1:1 and deposition gases of anargon gas at 30 sccm and an oxygen gas at 15 sccm. A deposition pressurewas 0.7 Pa (measured by Miniature Gauge MG-2 manufactured by CANONANELVA CORPORATION). A deposition power was 500 W. A substratetemperature was 300° C. A distance between the target and the substratewas 60 mm.

Next, heat treatment was performed at 450° C. under a nitrogenatmosphere for an hour. In addition, heat treatment was performed at450° C. under an oxygen atmosphere for an hour.

Then, a 20-nm-thick tungsten film was formed by a DC sputtering methodas a conductor to be the conductors 108 a and 108 b.

Next, a resist was formed over the conductor and the processing wasperformed using the resist, whereby the insulator 106 a, thesemiconductor 106 b, and island-shaped conductors were formed.

A resist was then formed over the island-shaped conductors, andprocessing was performed using the resist, whereby the conductors 108 aand 108 b were formed.

Next, a 5-nm-thick In—Ga—Zn oxide film was formed by a DC sputteringmethod to form an oxide to be the insulator 106 c using a target havingan atomic ratio of In:Ga:Zn=1:3:2 and deposition gases of an argon gasat 30 sccm and an oxygen gas at 15 sccm. A deposition pressure was 0.7Pa. A deposition power was 500 W. A substrate temperature was 200° C. Adistance between the target and the substrate was 60 mm.

A 10-nm-thick silicon oxynitride film was formed as an oxynitride to bethe insulator 112 by a PECVD method.

Then, as a conductor to be the conductor 114, a 10-nm-thick titaniumnitride film and a 30-nm-thick tungsten film were formed in this orderby a DC sputtering method. A resist was then formed over the conductorand processing was performed using the resist, whereby the conductor 114was formed.

Next, the above oxide and oxynitride were processed using the resistinto the insulator 106 c and the insulator 112.

After that, a 40-nm-thick aluminum oxide film was formed by an RFsputtering method as the insulator 116, using deposition gases of anargon gas at 25 sccm and an oxygen gas at 25 sccm. A deposition pressurewas 0.4 Pa. A deposition power was 2500 W. A substrate temperature was250° C. A distance between the target and the substrate was 60 mm.

Next, heat treatment was performed at 400° C. in an oxygen atmospherefor an hour.

A 150-nm-thick silicon oxynitride film was formed by a PECVD method.

Next, a 50-nm-thick titanium film, a 200-nm-thick aluminum film, and a50-nm-thick titanium film were formed in this order by a DC sputteringmethod. The films were processed using a resist to form the conductor120 a and the conductor 120 b.

Through the above steps, a transistor with a channel length L of 64 nmand a channel width W of 51 nm was fabricated as the sample 9A. By thesimilar method, a transistor with a channel length L of 43 nm and achannel width W of 44 nm was fabricated as the sample 9B.

In this example, potential was applied to a back gate (the conductor102) of each of the samples 9A and 9B in order to inject electrons intothe insulator 103, so that the threshold voltage of the transistor waschanged, as shown in FIG. 83E. The injection of electrons into theinsulator 103 was performed under the following conditions: a back-gatevoltage Vbg=40 V; a drain voltage Vd=0 V; a source voltage=0 V; and atop gate (the conductor 114) voltage Vg=0 V. Note that the back-gatevoltage was applied for 0 seconds, 0.4 seconds, 0.8 seconds, 1.2seconds, 1.6 seconds, 2.0 seconds, and 2.4 seconds, and the I_(d)-V_(g)characteristics under each electron-injection condition were measured.The I_(d)-V_(g) characteristics of the transistors were measured underthe following conditions: the back gate voltage was 0 V, the drainvoltage was 1.8 V, and the gate voltage was swept from −3.0 V to 3.0 Vin increments of 0.1 V.

FIGS. 83A and 83C show I_(d)-V_(g) characteristics of the samples 9A and9B. In each of FIGS. 83A and 83C, the horizontal axis represents gatevoltage V_(g) [V] and the vertical axis represents drain current I_(d)[A]. FIG. 83B shows the threshold voltage Vth and Shift of the sample 9Acalculated from the graph of FIG. 83A. Similarly, FIG. 83D shows thethreshold voltage V_(th) and Shift of the sample 9B calculated from thegraph of FIG. 83C.

FIGS. 83A to 83D show that in each of the samples 9A and 9B, thethreshold voltage was changed by injection of electrons into theinsulator 103 by applying potential to the back gate. It was also foundthat the threshold voltage can be controlled by changing the time forapplying voltage to the back gate.

This application is based on Japanese Patent Application serial No.2015-083163 filed with Japan Patent Office on Apr. 15, 2015 and JapanesePatent Application serial No. 2015-110541 filed with Japan Patent Officeon May 29, 2015, the entire contents of which are hereby incorporated byreference.

What is claimed is:
 1. A semiconductor device comprising a transistor,the transistor comprising: a first insulator; a second insulator overthe first insulator; an oxide semiconductor over an in contact with atleast a part of a top surface of the second insulator; a third insulatorover and in contact with at least a part of a top surface of the oxidesemiconductor; a first conductor and a second conductor electricallyconnected to the oxide semiconductor; a fourth insulator over the thirdinsulator; a third conductor over the fourth insulator, at least a partof the third conductor located between the first conductor and thesecond conductor; a fifth insulator over the third conductor, whereinthe first insulator includes a first silicon oxide film, a hafnium oxidefilm of the first silicon oxide film, and a second silicon oxide filmcontaining a halogen element over the hafnium oxide film, wherein a sidesurface of the second insulator and a side surface of the oxidesemiconductor overlap each other, and wherein the fifth insulator is incontact with the side surface of the second insulator, the side surfaceof the oxide semiconductor, and a top surface of the first insulator. 2.The semiconductor device according to claim 1, wherein a length of thethird insulator and a length of the fourth insulator are longer than alength of the third conductor in a channel length direction of thetransistor.
 3. The semiconductor device according to claim 1, whereinthe fifth insulator is in contact with a top surface and a side surfaceof the fourth insulator.
 4. A semiconductor device comprising atransistor, the transistor comprising: a first insulator; a secondinsulator over the first insulator; an oxide semiconductor over an incontact with at least a part of a top surface of the second insulator; athird insulator over and in contact with at least a part of a topsurface of the oxide semiconductor; a first conductor and a secondconductor electrically connected to the oxide semiconductor; a fourthinsulator over the third insulator; a third conductor over the fourthinsulator, at least a part of the third conductor located between thefirst conductor and the second conductor; a fifth insulator over thethird conductor, wherein the first insulator includes a first siliconoxide film, a hafnium oxide film of the first silicon oxide film, and asecond silicon oxide film containing fluorine over the hafnium oxidefilm, wherein a side surface of the second insulator and a side surfaceof the oxide semiconductor overlap each other, and wherein the fifthinsulator is in contact with the side surface of the second insulator,the side surface of the oxide semiconductor, and a top surface of thefirst insulator.
 5. The semiconductor device according to claim 4,wherein a length of the third insulator and a length of the fourthinsulator are longer than a length of the third conductor in a channellength direction of the transistor.
 6. The semiconductor deviceaccording to claim 4, wherein the fifth insulator is in contact with atop surface and a side surface of the fourth insulator.